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United States 
Environmental Protection 
M ^Agency 

The Occurrence of Disinfection 
By-Products (DBPs) of Health 
Concern in Drinking Water: 
Results of a Nationwide DBP 
Occurrence Study 






EPA/600/R-02/068 
September 2002 


The Occurrence of Disinfection By-Products (DBPs) 
of Health Concern in Drinking Water: 
Results of a Nationwide DBP Occurrence Study 


Howard S. Weinberg 

The Department of Environmental Sciences and Engineering 
University of North Carolina at Chapel Hill 
Chapel Hill, NC 

Stuart W. Krasner 

Metropolitan Water District of Southern California 
La Veme, CA 

Susan D. Richardson and Alfred D. Thruston, Jr. 
Ecosystems Research Division 
National Exposure Research Laboratory 
Office of Research and Development 
U.S. Environmental Protection Agency 
Athens, GA 



National Exposure Research Laboratory 
Office of Research and Development 
U.S. Environmental Protection Agency 
Athens, GA 



Recycled/Recyclable 

Printed with vegetable-based ink on 
paper that contains a minimum of 
50% post-consumer fiber content 
processed chlorine free. 


DISCLAIMER 


The United States Environmental Protection Agency (EPA) through its Office of 
Research and Development partially funded and collaborated in the research described here. The 
information in this document has been partially funded under Cooperative Agreement No. 
826697. It has been peer reviewed by the EPA and approved for publication. Mention of trade 
names or commercial products does not constitute endorsement or recommendation for use. 



LC Control Number 



2003 373312 


2 



















TABLE OF CONTENTS 


Acknowledgments.4 

Glossary of Terms.5 

Executive Summary.8 

Introduction.11 

Results 

EPA Region 9: Plants 1 and 2.22 

EPA Region 6: Plants 11 and 12.65 

EPA Region 4: Plants 7 and 8.121 

EPA Region 4: Plants 5 and 6.164 

EPA Region 3: Plants 3 and 4.214 

EPA Regions 5 and 7: Plants 9 and 10.270 

Conclusions.320 

Appendix.322 

Experimental Methods 

Chemical Standards.323 

Solid Phase Extraction-Gas Chromatography/Mass Spectrometry Method.343 

Liquid-Liquid Extraction-Gas Chromatography-Electron Capture Detection Method.365 

Closed-Loop Stripping Analysis Method.374 

Purge-and-Trap-Gas Chromatography/Mass Spectrometry Method.380 

Halogenated Furanones Method.393 

Carbonyl Method.429 

Broadscreen Gas Chromatography/Mass Spectrometry Procedure.444 

Mass Spectra for New Disinfection By-products Reported.448 

Mass Spectra for MX Analogues.455 


3 
























ACKNOWLEDGMENTS 


The authors would like to acknowledge the following people who contributed to this project. 

University of North Carolina 


Gretchen D. Onstad 

Ramiah Sangaiah 

Vanessa Pereira 

Gary L. Glish 

Karupiah Jayaraj 

Katrina Jamison 

Christine N. Dalton 

Lindsay Dubbs 

Zhengqi Ye 

Philip C. Singer 

Petra Strunk 


Metropolitan Water District of Southern California 


Alicia Gonzalez 

Lely Suhady 

Hsiao-Chiu Wang 

Salvador Pastor 

Jacob Nikonchuk 

Ching Kuo 

Russell Chinn 

Leslie Bender 

Suzanne Teague 

Michael J. Sclimenti 

Vaheh Martyr 

Robert Alvarez 

Sylvia Barrett 

Tim Albrecht 

Jesus Vasquez, Jr. 

Pat Hacker 

Bart Koch 

Eric Crofts 

Sikha Kundu 

Tiffany Lee 

Himansu Mehta 


U.S. EPA National Exposure Research Laboratory, Athens, GA 

Terrance L. Floyd 
F. Gene Crumley 

We also need to express appreciation to Leif Kronberg and Angel Messegauer for providing 
samples of furanone standards, as well as Bruce McKague (Can Syn Chem Co.), Francesc 
Ventura (Aigues of Barcelona, Spain) and George Majetich (Majestic Research) for providing 
standards for quantitative methods and new DBP identification work. 

Last, but not least, we would like to gratefully acknowledge the assistance of the participating 
utilities that collected the samples, provided operational and water quality data, and ensured a 
successful survey. Without their generous cooperation, this study would not have been possible. 

We are also extremely grateful to the U.S. EPA Office of Water and Office of Prevention, 
Pesticides, and Toxic Substances scientists who undertook the initial DBP prioritization effort 
that provided the focus for this study. Thank you to Vicki Dellarco, Yin-Tak Woo, David Lai, 
Jennifer McLain, and Mary Ko Manibusan. 


4 


GLOSSARY OF TERMS 


AOC 

BEMX 

BF 3 /MeOH 

BMX-1 

BMX-2 

BMX-3 

CCF 

ch 2 n 2 

Cl 

C1 2 

CLSA 

cio 2 

C10 2 ' 

CT 

DC AN 

DIW 

DBP 

DCP 

DOC 

DS 

DXAA 

EBCT 

ECD 

El 

EMX 

EtAc 

FE 

FI 

GAC 

GC 

H 2 S0 4 /Me0H 

HAAs 

HAA5 

Assimilable organic carbon 

Brominated forms of EMX 

Boron trifluoride methanol complex 
3-Chloro-4-(bromochloromethyl)-5-hydroxy-2(5H)-furanone 
3-Chloro-4-(dibromomethyl)-5-hydroxy-2(5H)-furanone 
3-Bromo-4-(dibromomethyl)-5-hydroxy-2(5H)-fiiranone 

Carbon contactor filtered 

Diazomethane 

Chemical ionization 

Chlorine 

Closed-loop stripping analysis 

Chlorine dioxide 

Chlorite 

Concentration-time 

Dichloroacetonitrile 

Deionized water 

Disinfection by-product 

Dichloropropanone 

Dissolved organic carbon 

Distribution system 

Sum of dihaloacetic acids (dichloro-, bromochloro-, dibromoacetic acid) 
Empty bed contact time 

Electron capture detector 

Electron ionization 

(E)-2-Chloro-3-(dichloromethyl)-4-oxobutenoic acid 

Ethyl acetate 

Filter effluent 

Filter influent 

Granular activated carbon 

Gas chromatography or Gas chromatograph 

Sulfuric acid in methanol 

Haloacetic acids 

Sum of 5 HAAs (monochoro-, monobromo-, dichloro-, dibromo-, 
trichloroacetic acid) 

HAA9 

Sum of 9 HAAs (HAA5 + bromochloro-, bromodichloro-, 
dibromochloro-, tribromoacetic acid) 

HANs 

Haloacetonitriles 


5 


HKs 

Haloketones 

HNMs 

Halonitromethanes 

HPLC 

High performance liquid chromatography 

HRMS 

High resolution mass spectrometry 

ICR 

Information Collection Rule 

ID 

Inner diameter 

IS 

Internal standard 

KHP 

Potassium hydrogen phosphate 

LLE 

Liquid-liquid extraction 

MBA 

Mucobromic acid 

MCA 

Mucochloric acid 

MCL 

Maximum contaminant level 

MDL 

Method detection limit 

MEK 

Methyl ethyl ketone 

MeOH 

Methanol 

MG 

Million gallons 

mgd 

Million gallons per day 

MS 

Mass spectrometry 

MtBE 

Methyl tertiary -butyl ether 

MW 

Molecular weight 

MWDSC 

Metropolitan Water District of Southern California 

MX 

3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone 

MX-analogues 

MX, ZMX, EMX, ox-MX, ox-EMX, red-MX, MCA, BMX-1,2,3 

MXR 

Esterified form of MX 

MXR-analogues 

Esterified forms of MX-analogues 

NA 

Not available 

ND 

Not detected at or above minimum reporting level (MRL) 

NH 2 C1 

Chloramines 

NMR 

Nuclear magnetic resonance 

NR 

Not reported 

NS 

Not sampled 

n 2 

Nitrogen gas 

nh 3 

Ammonia 

NOM 

Natural organic matter 

0 3 

Ozone 

OE 

Ozone contactor effluent 

Ox-EMX 

Oxidized EMX, (E)-2-Chloro-3-(dichloromethyl)butenedioic acid 

Ox-MX 

Oxidized MX, (Z)-2-Chloro-3-(dichloromethyl)butenedioic acid 

Ox-NOM 

Oxidized NOM 

PE 

Plant effluent 

PFBHA 

Pentafluorobenzylhydroxylamine 


6 


P&T 

Red-MX 

RDL 

RM 

SDS 

SIR 

SPE 

SPME 

SUVA 

TCP 

THMs 

THM4 

TIC 

TLC 

TOC 

TT 

TXAA 

UNC 

USEPA 

UV 

voc 

WTP 

ZMX 


Purge-and-trap 

Reduced MX, 3-Chloro4-(dichloromethyl)-2(5H)-furanone 
Reporting detection level 
Rapid mix 

Simulated distribution system 
Selected ion monitoring 
Solid phase extraction 
Solid phase microextraction 
Specific ultraviolet absorbance 
Trichloropropanone 
Trihalomethanes 

Sum of 4 regulated THMs (chloroform, bromoform, 
bromodichloromethane, dibromochloromethane) 

Total ion chromatogram 
Thin layer chromatography 
Total organic carbon 
Treatment tank effluent 

Sum of trihaloacetic acids (trichloro-, bromodichloro-, dibromochloro-, 
tribromoacetic acid) 

University of North Carolina 

United States Environmental Protection Agency 

Ultraviolet light 

Volatile organic compound 

Water treatment plant 

(Z)-2-Chloro-3-(dichloromethyl)-4-oxobutenoic acid 


7 


EXECUTIVE SUMMARY 


The motivation for this Nationwide Disinfection By-product (DBP) Occurrence Study 
was two-fold: First, more than 500 DBPs have been reported in the literature, yet there is almost 
no quantitative occurrence information for most. As a result, there is significant uncertainty over 
the identity and levels of DBPs that people are exposed to in their drinking water. Second, only 
a limited number of DBPs have been studied for adverse health effects. So, it is not known 
whether other DBPs (besides the few that are currently regulated) pose a risk to human health. 

To determine whether other DBPs pose an adverse health risk, more comprehensive quantitative 
occurrence and toxicity data are needed. 

Because health effects studies are very expensive, it is not possible to test all DBPs that 
have been reported. It is also not feasible to measure >500 DBPs in waters across the United 
States. Thus, results of a DBP prioritization effort by scientists at the U.S. Environmental 
Protection Agency (USEPA) Office of Water and the USEPA Office of Prevention, Pesticides, 
and Toxic Substances were used to focus this study on those DBPs that were the most 
toxicologically significant. These EPA experts applied an in-depth mechanism-based structural 
activity relationship analysis to the more than 500 DBPs reported in the literature, supplemented 
by an extensive literature search for genotoxicity and other data, and ranked the carcinogenic 
potential of these DBPs. Approximately 50 DBPs that received the highest ranking for potential 
toxicity and that were not included in the USEPA’s Information Collection Rule (ICR) were 
selected for this occurrence study. These DBPs, denoted as ‘high priority’ DBPs in this report, 
included such compounds as MX [3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-fiiranone], 
brominated forms of MX (BMXs), halonitromethanes, iodo-trihalomethanes, and many 
brominated species of halomethanes, haloacetonitriles, haloketones, and haloamides. 

For this Nationwide Occurrence Study, scientists from the USEPA’s National Exposure 
Research Laboratory (NERL) initiated a collaboration with scientists at the University of North 
Carolina (UNC, Howard Weinberg, PI) and the Metropolitan Water District of Southern 
California (MWDSC, Stuart Krasner, co-PI). The ‘high priority’ DBPs, along with regulated and 
Information Collection Rule DBPs for comparison, were quantified in drinking waters across the 
United States. These waters represented diverse geographic regions with different source water 
quality. Several source waters contained relatively high bromide levels (where brominated 
DBPs would be expected to form). In addition, many of the waters selected for study were 
relatively high in total organic carbon (TOC). Waters treated with all four major disinfectants 
(chlorine, chloramines, ozone, and chlorine dioxide) were studied. In addition, the fate and 
transport of these DBPs was studied in the real distribution systems and in simulated distribution 
system (SDS) tests. Prior to this study, there was almost nothing known about the stability of 
these DBPs in the distribution system. 

Because no quantitative analytical methods existed for most of the high priority DBPs, 
optimized analytical methods were initially developed at UNC and MWDSC. No one single 
analytical method could be used for all DBPs, so different methods were developed and 
optimized for specific groups of DBPs. Also, because there were no commercially available 
standards for many of these compounds, many had to be synthesized. 


8 


Another goal of this project was to use this opportunity to look for other DBPs that have 
not been previously identified in order to provide a more complete assessment of DBPs formed 
by different treatments in different regions of the United States. This work was carried out at the 
USEPA NERL- Athens laboratory. For this research, a combination of advanced mass 
spectrometric tools was used to identify the new DBPs. 

Results revealed the presence of many of the high priority DBPs in the waters sampled. 
Important observations included finding the highest levels of iodo-trihalomethanes (THMs) at a 
plant that used chloramination without pre-chlorination. Levels of individual iodo-THMs ranged 
from 0.2 to 15 pg/L. Another important observation involved finding the highest concentration 
of dichloroacetaldehyde at a plant that used chloramine and ozone disinfection. Therefore, 
although the use of alternative disinfectants minimized the formation of the four regulated 
THMs, certain dihalogenated DBPs and iodo-THMs were formed at significantly higher levels 
than in waters treated with chlorine. Thus, the formation and control of the four regulated THMs 
is not necessarily an indicator of the formation and control of other halogenated DBPs, and the 
use of alternative disinfectants does not necessarily control the formation of all halogenated 
DBPs, and can even result in increased concentrations of some. Moreover, many of these 
halogenated DBPs—including certain dihalogenated and brominated species—were not studied 
in the ICR 

Halogenated furanones, including MX and brominated MX (BMX) analogues, were 
widely observed in these samplings. Another finding was the high levels of MX and MX- 
analogues in many samples. It was previously observed that MX did not exceed a concentration 
of 60 to 90 ng/L (the few measurements that had been conducted generally showed levels <60 
ng/L). In this study, however, MX was often observed at levels significantly greater than 100 
ng/L, with a maximum level of 310 ng/L observed in finished water from a treatment plant that 
disinfected a high-TOC water with chlorine dioxide, chlorine, and chloramines. These findings 
are significant because the levels of MX are much higher than previously reported. Likewise, 
several other analogues of MX were identified, including BMX analogues. Results include 170 
ng/L and 200 ng/L levels for BMX-1 and BEMX-3, respectively (at a treatment plant that 
disinfected a high-bromide water with chlorine dioxide, chlorine, and chloramines). It is 
interesting that the drinking water utilities with the highest MX and BMX levels were from 
treatment plants that use chlorine dioxide for primary disinfection. MX did not form from 
chlorine dioxide disinfection per se, rather chlorine dioxide oxidation appeared to not destroy 
MX precursors (as ozone, another alternative disinfectant, does). Thus, MX and BMX formation 
was highest at treatment plants with high levels of TOC and bromide, respectively. 

Halonitromethanes, including dihalogenated and brominated species not included in the 
ICR, were found in some of the samples; levels of individual species ranged from 0.1 to 3 pg/L. 

In some cases, pre-ozonation was found to increase the formation of the trihalonitromethanes 
(brominated analogues of chloropicrin [trichloronitromethane]). Many brominated acids were 
also identified in several finished waters that contained elevated levels of bromide in their source 
waters. A number of brominated acids were identified for the first time (i.e., brominated 
propanoic, propenoic, butanoic, butenoic, oxopentanoic, heptanoic, nonanoic, and butenedioic 
acids), with most being observed in the finished water from a treatment plant that has significant 


9 


bromide levels in its source water. One of the high priority DBPs, 3,3-dichloropropenoic acid, 
was found in several finished waters, giving further evidence that haloacids with longer carbon 
chains are prevalent DBPs (i.e., haloacetic acids are not the only haloacids formed during 
disinfection). 

Dihaloacetaldehydes and brominated analogues of chloral hydrate 
(trichloroacetaldehyde) were detected in many samples, as were mono-, di-, tri-, and/or tetra- 
species of halomethanes and haloketones. Several haloamides were also found in finished waters 
at levels similar to DBPs that are commonly measured (low pg/L levels). This is a class of DBPs 
that has not been previously quantified, but the levels observed in this study indicate that then- 
levels in finished waters are not trivial. In addition, carbon tetrachloride was detected in some of 
the waters measured, with a maximum of 0.8 pg/L observed. Although carbon tetrachloride was 
present in sampled finished drinking waters, its identity as a DBP could not be proven, since 
carbon tetrachloride is sometimes used to clean out chlorine cylinders before they are filled. 

Thus, it could be either a DBP or a contaminant from the cleaning process. 

Another finding in this study was the discovery of iodoacids for the first time. Five new 
iodoacid species were tentatively identified: iodoacetic acid, iodobromoacetic acid, 
iodobromopropenoic acid (2 isomers), and 2-iodo-3-methylbutenedioic acid. High resolution 
mass spectrometry confirmed the presence of iodine in their structures and the overall empirical 
formulas for these new DBPs. One of these—iodoacetic acid—has been confirmed through the 
analysis of an authentic chemical standard (match of retention time and mass spectrum). 
Additional synthetic standards are currently being prepared to confirm the other iodoacid 
identifications. These iodoacids were observed as DBPs in a high-bromide water from a 
treatment plant that uses only chloramine disinfection. Another iodinated DBP, tentatively 
identified as iodobutanal, was found in finished waters from treatment plants on both coasts that 
can be impacted by saltwater intrusion (sea water is a source of iodide in addition to a major 
source of bromide in some drinking waters). This DBP has also not been reported previously. 

In addition to the new iodinated DBPs and new brominated acids, another brominated 
ketone was identified for the first time: 1-bromo-1,3,3-trichloropropanone, which was found in 
many of the waters sampled. 

The stability of DBPs in actual distribution systems and in simulated distribution system 
(SDS) tests varied. In most cases where chloramination was used, the DBPs were relatively 
stable. However, when free chlorine was used, THMs and other DBPs, including haloacetic 
acids, increased in concentration both in the actual distribution system and in SDS tests. 
Haloacetonitriles generally were stable (at the distribution-system pH levels encountered in this 
study) and increased in concentration, but many of the haloketones were found to degrade in the 
distribution system and SDS tests. Halonitromethanes and dihaloacetaldehydes were found to be 
stable in these systems and tests. Although controlled laboratory studies had suggested 
instability of halogenated furanones, particularly MX, in water, MX and MX-analogues were 
sometimes stable, and sometimes they degraded somewhat in the distribution systems and SDS 
tests. When the MX analogues showed some degradation in the distribution system, they were 
generally still present at detectable levels, indicating that they do not completely degrade in the 
distribution system. Many times, the BMXs were stable. 


10 


INTRODUCTION 


More than 500 disinfection by-products (DBPs) have been reported in the literature for 
the major disinfectants currently used (chlorine, ozone, chlorine dioxide, chloramines), as well as 
their combinations (Richardson, 1998). Of these reported DBPs, only a small percentage have 
been quantified in drinking waters. Thus, there is significant uncertainty over the identity and 
levels of DBPs that people are actually exposed to in their drinking water. Moreover, only a 
limited number of DBPs have been studied for adverse health effects. To determine whether the 
other DBPs pose an adverse health risk, more comprehensive quantitative occurrence and 
toxicity data are needed. To address this issue, scientists at the U.S. Environmental Protection 
Agency’s (USEPA’s) National Exposure Research Laboratory (NERL) initiated a proposal for a 
Nationwide DBP Occurrence Study. 

Due to the large number of DBPs identified in drinking waters in the United States and 
other countries, it is not feasible to quantify all of them, so a way of prioritizing them was 
needed. Prior to this occurrence study, a multidisciplinary group of experts from the USEPA 
Office of Water and the USEPA Office of Prevention, Pesticides, and Toxic Substances had 
initiated a prioritization effort for the >500 DBPs reported in the literature according to their 
predicted adverse health effects (Woo et al., 2002). An in-depth, mechanism-based, structural 
activity relationship (SAR) analysis, supplemented by an extensive literature search for 
genotoxicity and other data, was used to rank the carcinogenic potential of these DBPs. 
Approximately 50 DBPs that received the highest ranking for potential toxicity, and that were 
not already included in the USEPA’s Information Collection Rule (ICR), were selected for this 
occurrence study. Those ~50 DBPs are denoted ‘high priority’ DBPs in this report. 

The ‘high priority’ DBPs include brominated, chlorinated, and iodinated species of 
halomethanes, brominated and chlorinated forms of haloacetonitriles, haloketones, haloacids, 
and halonitromethanes, as well as analogues of MX [3-chloro-4-(dichloromethyl)-5-hydroxy- 
2(5H)-fiiranone] (Table 1). Chemical Abstract Services (CAS) numbers are provided in Table 1 
when they were available. Previously, MX had been determined to be the most mutagenic (to 
Salmonella bacteria) DBP ever identified in drinking water, accounting for as much as 20-50% 
of the total mutagenic activity measured in chlorinated drinking water samples (Kronberg and 
Vartiainen, 1988; Backlund et al., 1988; Meier et al., 1987). MX has also been shown to be 
carcinogenic in laboratory animals (Komulainen et al., 1997). Yet, very little drinking water 
occurrence data has been obtained for MX, so its potential hazard to humans has not been 
determined. There have also been recent reports of brominated DBP forms of MX (BMXs) 
(Suzuki and Nakanishi, 1995). These brominated DBP species are of concern because 
brominated species of DBPs have been shown to be significantly more carcinogenic than their 
chlorinated analogues. Brominated nitromethanes have also been recently shown to be 
extremely cytotoxic and genotoxic in mammalian cells (Plewa et al., 2002; Kargalioglu et al., in 
press). Specifically, they have been shown to be at least an order of magnitude more genotoxic 
to mammalian cells than MX and have genotoxicities greater than all of the regulated DBPs, 
except for monobromoacetic acid. It is interesting that dibromonitromethane and 


11 


bromonitromethane received the highest priority ranking of all DBPs in the SAR toxicity 
analysis effort. 

It should be noted that Table 1 lists the identity of more than 50 high priority target 
species. During method development, additional species in the same analyte group were 
included for some of the drinking water plant surveys. 

Because most of the high priority DBPs were from chlorine or chloramine disinfection, a 
few additional ozone and chlorine dioxide DBPs that were not ranked as a high priority were also 
included for completeness (i.e., to provide more information on those alternative disinfectants). 

In addition, methyl tert -butyl ether (MtBE) and methyl bromide, which are volatile organic 
compounds (VOCs) but not DBPs, were included in the list of target analytes because they are 
important source water pollutants, and their measurement would provide valuable occurrence 
information. Regulated and some ICR DBPs were also included in this study for comparison 
purposes (Table 2). In addition, routine water quality measurements, such as total organic 
carbon (TOC), total organic halide (TOX), assimilable organic carbon (AOC), and bromide were 
determined. 


12 


Table 1. Priority DBPs selected for Nationwide Occurrence Study a 

MX and MX-Analogues: 

3 - Chloro- 4 - (dichloromethyl) - 5 - hydroxy- 2 (5 H)- furanone (MX) 

3 - Chloro- 4- (dichloromethyl) - 2 - (5 H)- fUranone (red- MX) 
(E)-2-Chloro-3-(dichloromethyl)-butenedioic acid (ox-MX) 
(E)-2-Chloro-3-(dichloromethyl)-4-oxobutenoic acid (EMX) 

2.3- Dichloro-4-oxobutenoic acid (Mucochloric acid) [87-56-9] 
3-Chloro-4-(bromochloromethyl)-5-hydroxy-2(5H)-furanone (BMX-1) [132059-51-9] 
3 - Chloro- 4- (dibromomethyl)- 5 - hydroxy- 2(5H)- furanone (BMX- 2) [132059-52-0] 
3-Bromo-4-(dibromomethyl)-5-hydroxy-2(5H)-furanone (BMX-3) [132059-53-1] 
(E)-2-Chloro-3-(bromochloromethyl)-4-oxobutenoic acid (BEMX-1) c 
(E)-2-Chloro-3-(dibromomethyl)-4-oxobutenoic acid (BEMX-2) c 
(E)-2-Bromo-3-(dibromomethyl)-4-oxobutenoic acid (BEMX-3) c 

Haloacids: 

3.3- Dichloropropenoic acid 

Halomethanes: 

Chloromethane [74- 87-3] 

Bromomethane (methyl bromide) [74-83-9] b 
Dibromomethane [74-95-3] 

Bromochloromethane [74-97-5] 

Bromochloroiodomethane [34970-00-8] 

Dichloroiodomethane [594-04-7] 

Dibromoiodomethane c [593-94-2] 

Chlorodiiodomethane c [638-73-3] 

Bromodiiodomethane c [557-95-9] 

Iodoform [75-47-8] c 
Chlorotribromomethane [594-15-0] 

Carbon tetrachloride [56-23-5] 

Halonitromethanes: 

Bromonitromethane [563-70-2] 

Chloronitromethane c [1794-84-9] 

Dibromonitromethane [598-91-4] 

Dichloronitromethane c [7119-89-3] 

Bromochloronitromethane c [135531-25-8] 

Bromodichloronitromethane c [918-01-4] 

Dibromochloronitromethane c [1184-89-0] 

Tribromonitro m e th a ne (brom o p icri n) c \ 4 6 4- 10-8]. 


13 







Table 1 (Continued) 

Haloacetonitriles: 


Bromoacetonitrile [590-17-0] 
Chloroacetonitrile [107-14-2] 
Tribromoacetonitrile [75519-19-6] 
Bromodichloroacetonitrile [60523-73-1] 
Dibromochloroacetonitrile [ 144772- 39-4] 

Haloketones: 

Chloropropanone [78-95-5] 

1.3- Dichloropropanone [534-07-6] 

1,1 -Dibromopropanone 

1.1.3- Trichloropropanone [921-03-9] 

1 -Bromo-1,1 -dichloropropanone 

1.1.1.3- Tetrachloropropanone [16995-35-0] 

1.1.3.3- Tetrachloropropanone [632-21-3] 

1.1.3.3- Tetrabromopropanone c [22612-89-1] 

1.1.1.3.3- Pentachloropropanone [1768-31-6] 
Hexachloropropanone [116-16-5] 

Haloaldehydes: 

Chloroacetaldehyde [107-20-0] 
Dichloroacetaldehyde [70-02-7] 
Bromochloroacetaldehyde c [98136-99-3] 
Tribromoacetaldehyde [115-17-3] c 

Haloacetates: 

Bromochloromethyl acetate [247943-54-0] 
Haloamides: 

Monochloroacetamide [79-07-2] c 
Monobromoacetamide [683-57-8] c 
Dichloroacetamide [683-72-7] 
Dibromoacetamide c [598-70-9] 
Trichloroacetamide [594-65-0] c _ 


14 









Table 1 (Continued) 

Non-Halo genated Aldehydes and Ketones: 

2-Hexenal [505-57-7]; [6728-26-3] 

5- Keto- 1-hexanal d 
Cyanoformaldehyde [4471-47-0] 

Methylethyl ketone (2-butanone) [78-93-3] d 

6- Hydroxy-2-hexanone d 
Dimethylglyoxal (2,3-butanedione) [431-03-8] 

Volatile organic compounds (VOCs) and Miscellaneous DBPs: 

1.1.1.2- Tetrabromo-2-chloroethane 

1.1.2.2- Tetrabromo-2-chloroethane c 
Methyl- tert -butyl ether [1634-04-4] b 

Benzyl chloride [100-44-7] _ 

a Chemical Abstracts Services (CAS) numbers provided in brackets when available. 
b Not a DBP, but included because it is an important source water contaminant. 
c DBP not originally prioritized (identified in drinking water after initial prioritization), but 
included due to similarity to other priority compounds. 

d DBP not given a high priority, but included for completeness sake to provide more 
representation to ozone DBPs for occurrence. 


Table 2. Information Collection Rule and regulated DBPs included for comparison a 


Halomethanes 

Haloacetic acids (cont). 

Chloroform 

Dibromoacetic acid 

Bromodichloromethane 

Trichloroacetic acid 

Dibromochloromethane 

Bromodichloroacetic acid 

Bromoform 

Dibromochloroacetic acid 


Tribromoacetic acid 

Haloacetonitriles 


Dichloroacetonitrile 

Halonitromethanes 

Bromochloroacetonitrile 

Chloropicrin (trichloronitromethane) 

Dibromoacetonitrile 


Trichloroacetonitrile 

Haloaldehvdes 


Chloral hydrate 

Haloketones 

(trichloroacetaldehyde) 

1,1 -Dichloropropanone 


1,1,1 -Trichloropropanone 

Oxvhalides 


Bromate 

Haloacetic acids 

Chlorate 

Monochloroacetic acid 

Chlorite 

Monobromoacetic acid 


Dichloroacetic acid 


Bromochloroacetic acid 



a Five HAAs are regulated; six HAAs were required in the ICR, however some utilities reported 
data on the complete set of 9 HAAs. 


15 















The design of this study involved the study of drinking waters disinfected with the four 
common disinfectants: chlorine, chloramines, ozone, and chlorine dioxide. Because many of the 
high priority DBPs were brominated, it was important to include drinking waters that contained 
relatively high bromide levels. In addition, many of the waters selected for study were relatively 
high in TOC. Drinking water samples were selected from across the United States to assess the 
distribution and speciation of by-products in a variety of different waters from geographically 
diverse regions, with differing water quality, treatment, and distribution system characteristics 
(Figure 1). Moreover, pairs of treatment plants were chosen that used source waters from the 
same (or similar) watersheds but employed different treatment technologies and disinfection 
scenarios. This permitted an evaluation of the impact of technology and disinfectant 
combinations on by-product formation, while minimizing confounding factors related to 
differing source water quality. Each of the plants provided operational information and 
complementary water quality analyses. Drinking water was also sampled at typically two points 
in each distribution system to determine the fate and transport of DBPs—as well as actual 
occurrence in the distribution system—and simulated distribution system (SDS) tests were 
conducted to determine the formation and stability of DBPs in the presence of chlorine or 
chloramines. Previously, most of the newly identified DBPs were detected in drinking waters 
that had been sampled only at the treatment plant; very little was known about the fate and 
transport (and stability) of most of the newly identified DBPs in the distribution system. To this 
end, the influence of water quality parameters, treatment, and distribution system conditions on 
DBP concentrations and persistence (stability) was a major objective of this work. The drinking 
water utilities that were sampled are shown in Table 3. 


16 


Sampling Survey: 12 plants sampled quarterly 
2 plants - same watershed - different treatment/disinfection 


Plants sampled in EPA Regions 3, 4, 5, 6, 7, and 9 



NH 
M A 


...other Region 9 sites 


...other Region 2 sites 


«► Guam 


«► Puerto Rico 


** American Samoa 


Virgin Islands 


•►Trust Territories 




*► Commonwealth of the Northern Mariana Islands 


Figure 1. Sampling survey. 


Table 3. Drinking water utilities sampled 


Utility 1 (EPA Region 5 ) 

Disinfection Used 

Plant 1 (EPA Region 9) 

Ozone - chlorine - chloramines 

Plant 2 (EPA Region 9) 

Chlorine- chloramines 

Plant 12 (EPA Region 6) 

(Chlorine dioxide-)Chloramines 

Plant 11 (EPA Region 6) 

Chlorine dioxide- chlorine - chloramines 

Plant 8 (EPA Region 4) 

Chlorine- chloramines 

Plant 7 (EPA Region 4) 

Chloramines- ozone 

Plant 6 (EPA Region 4) 

Chlorine dioxide-chlorine-chloramines 

Plant 5 (EPA Region 4) 

Ozone-chlorine 

Plant 3 (EPA Region 3) 

Chlorine- chloramines 

Plant 4 (EPA Region 3) 

Chlorine 

Plant 10 (EPA Region 5) 

Chlorine - chloramines 

Plant 9 (EPA Region 7) 

Chlorine- chloramines 


17 




































a The following pairs of plants treated water from the same or similar watersheds: plants land 2; 
3 and 4; 5 and 6; 7 and 8; 9 and 10; and 11 and 12. 

b The 12 plants in this survey were located in six of the nine regions defined by the EPA. The 
states included in each of these six regions are as follows: 

EPA Region 9—Arizona, California Hawaii, Nevada 

EPA Region 6—Arkansas, Louisiana, New Mexico, Oklahoma, Texas 

EPA Region 4—Alabama, Florida, Georgia, Kentucky, Mississippi, North Carolina, South 
Carolina, Tennessee 

EPA Region 3—Delaware, Maryland, Pennsylvania, Virginia, West Virginia, Washington 
D.C. 

EPA Region 5—Illinois, Indiana, Michigan, Minnesota, Ohio, Wisconsin 
EPA Region 7—Iowa, Kansas, Missouri, Nebraska 


Because there were no existing quantitative analytical methods for most of the high 
priority DBPs, methods were initially developed at UNC and MWDSC. The high priority DBPs 
were divided between UNC and MWDSC for method development and quantitative analyses 
(UNC measured the MX analogues, carbonyls, 3,3-dichloropropenoic acid, haloacetates, 
haloamides, and some haloaldehydes; MWDSC measured bromate, chlorate, chlorite, 
halomethanes, haloacetic acids, haloacetonitriles, haloacetaldehydes, haloketones, 
halonitromethanes, methyl ethyl ketone, methyl tertiary butyl ether (MTBE), 
tetrabromochloroethane, and benzyl chloride). In addition, a method was used at UNC for 
differentiating the total organic chlorine and bromine. No one single analytical method could be 
used for all DBPs, so different methods were developed and optimized for specific groups of 
DBPs. Also, because there were no commercially available standards for many of these 
compounds, a significant number had to be synthesized. A combination of extraction and 
derivatization techniques were utilized that minimized artifact formation and maximized 
recovery of the target analytes from the aquatic matrix. Positive identification was achieved 
through use of a combination of complementary spectroscopic tools, some of which were 
designed to target a broader range of by-products than those listed, and/or dual-column gas 
chromatography. Once methods for the target by-products were established, studies of their 
formation and stability were conducted at full-scale treatment plants and their respective 
distribution systems. 

Another goal of this project was to use this opportunity to look for other DBPs that had 
not been previously identified in order to provide a more complete assessment of DBPs formed 
by different treatments in different regions of the U.S. This work was carried out at the USEPA 
NERL- Athens laboratory. For this research, a combination of mass spectrometric techniques 
(gas chromatography with high and low resolution electron ionization mass spectrometry, and 
with chemical ionization mass spectrometry) was used to aid in the identification of these new 
DBPs. Mass spectra for those DBPs that had not been previously reported (i.e., those identified 
in this study for the first time) are provided in the Appendix of this report. 

Presentations of preliminary results from this Nationwide DBP Occurrence Study have 
been given at several scientific meetings over the last three years. Citations of the more 
comprehensive proceedings articles appear below for reference (Krasner et al., 2002; Sclimenti 


18 


et al., 2002; Krasner et al., 2001; Weinberg et al., 2001; Gonzalez et al., 2000; Onstad et al., 
2000, Onstad and Weinberg, 2001). 


This report is presented in multiple chapters, each of which represents a specific 
component of the research, method development, and DBP analysis in the treatment plants after 
different unit processes and/or disinfectant addition and in the distribution systems. 


19 


REFERENCES 


Backhand, P., L. Kronberg, and L. Tikkanen. Formation of Ames mutagenicity and of the strong 
bacterial mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone and other halogenated 
compounds during disinfection of drinking water. Chemosphere 17(7): 1329 (1988). 


Gonzalez, A. C., S. W. Krasner, H. Weinberg, and S. D. Richardson. Determination of newly 
identified disinfection by-products in drinking water. Proceedings of the American Water Works 
Association Water Quality Technology Conference , American Water Works Association: 

Denver, CO, 2000. 

Kargalioglu, Y., E. D. Wagner, S. D. Richardson, and M. J. Plewa. DNA damage in the 
CHO/Comet assay induced by nitrohalomethanes, a novel class of drinking water disinfection 
by-products. Environmental Science & Technology (in press). 

Komulainen, H., V.-M. Kosma, S.-L. Vaittinen, T. Vartiainen, E. Kaliste-Korhonen, S. Lotjonen, 

R. K. Tuominen, and J. Tuomisto. Carcinogenicity of the drinking water mutagen 3-chloro-4- 
(dichloromethyl)-5-hydroxy-2(5H)-furanone in the rat. Journal of the National Cancer Institute 
89(12): 848 (1997). 


Krasner, S. W., R. Chinn, S. Pastor, M. J. Sclimenti, S. D. Richardson, A. D. Thruston, Jr., and 
H. S. Weinberg. Relationships between the different classes of DBPs: formation, speciation, and 
control. Proceedings of the American Water Works Association Water Quality Technology 
Conference, American Water Works Association: Denver, CO, 2002. 

Krasner, S. W., S. Pastor, R. Chinn, M. J. Sclimenti, H. S. Weinberg, and S. D. Richardson. The 
occurrence of a new generation of DBPs (beyond the ICR). Proceedings of the American Water 
Works Association Water Quality Technology Conference, American Water Works Association: 
Denver, CO, 2001. 

Kronberg, L., and T. Vartiainen. Ames mutagenicity and concentration of the strong mutagen 3- 
chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-fiiranone and of its geometric isomer E-2-chloro-3- 
(dichloromethyl)-4-oxo-butenoic acid in chorine-treated tap waters. Mutation Research 206:177 
(1988). 


Meier, J. R., R. B. Knohl, W. E. Coleman, H. P. Ringhand, J. W. Munch, W. H. Kaylor, R. P. 
Streicher, and F. C. Kopfler. Studies on the potent bacterial mutagen, 3-chloro-4- 
(dichloromethyl)-5-hydroxy-2(5H)-furanone: aqueous stability, XAD recovery and analytical 
determination in drinking water and in chlorinated humic acid solutions. Mutation Research 
189:363 (1987). 


Onstad, G. D., H. S. Weinberg, S. W. Krasner, and S. D. Richardson. Evolution of analytical 
methods for halogenated fiiranones in drinking water. Proceedings of the American Water 


20 


Works Association Water Quality Technology Conference, American Water Works Association: 
Denver, CO, 2000. 

Onstad, G. D., and H. S. Weinberg. Improvements in extraction of MX-analogues from drinking 
water. Proceedings of the American Water Works Association Water Quality Technology 
Conference, American Water Works Association: Denver, CO, 2001. 

Plewa, M. J., E. D. Wagner, and S. D. Richardson. Quantitative comparative mammalian cell 
cytotoxicity and genomic genotoxicity of drinking water disinfection by-products. Paper 
presented at the International Society of Exposure Analysis (ISEA)-International Society for 
Environmental Epidemiology (ISEE) Conference, Vancouver, Canada, August 11-15, 2002. 

Richardson, S. D. Drinking water disinfection by-products. In The Encyclopedia of 
Environmental Analysis and Remediation (R.A. Meyers, ed.), Vol. 3, John Wiley & Sons: New 
York, 1998, pp.1398-1421. 


Sclimenti, M. J., S. W. Krasner, and S. D. Richardson. The determination of DBPs using a solid 
phase microextraction (SPME)-GC/ECD technique. Proceedings of the American Water Works 
Association Water Quality Technology Conference, American Water Works Association: 
Denver, CO, 2002. 

Suzuki, N., and J. Nakanishi. Brominated analogues of MX (3-chloro-4-(dichloromethyl)-5- 
hydroxy-2(5H)-furanone in chlorinated drinking water. Chemosphere 30(8): 1557 (1995). 


Weinberg, H. S., S. W. Krasner, and S. D. Richardson. Determination of new carbonyl- 
containing disinfection by-products in drinking water. Proceedings of the American Water 
Works Association Water Quality Technology Conference, American Water Works Association: 
Denver, CO, 2001. 

Woo, Y.-T., D. Lai, J. L. McLain, M. K. Manibusan, and V. Dellarco. Use of mechanism-based 
structure-activity relationships analysis in carcinogenic potential ranking for drinking water 
disinfection by-products. Environmental Health Perspectives 110(Suppl. 1):75 (2002). 


21 


RESULTS 


EPA REGION 9: PLANTS 1 AND 2 
Plant Operations and Sampling 

On October 30, 2000, January 23, 2001, July 17, 2001, and March 19, 2002, two 
treatment plants in EPA Region 9 were sampled. 

The treatment processes at plant 1 (Figure 1) included ozonation, flocculation, 
coagulation, sedimentation, and filtration. A secondary disinfectant was not applied until after 
the filters, so the filters were operated biologically. After the filters, the water was chlorinated 
with a short, free chlorine contact time, and then ammonia was added to form chloramines. 

Note, the basins at plant 1 were chlorinated (using sodium hypochlorite) on average twice per 
week for approximately four hours. This chlorine was applied to the effluent of the ozone 
contactors to help control algae and other growths in the basins. 

Plant 1 was sampled at the following locations: 

(1) raw water before the ozone contactor 

( 2 ) the ozone (O 3 ) contactor effluent 

(3) the filter influent 

(4) the filter effluent 

(5) the clearwell effluent 

(6) the finished water 

The treatment processes at plant 2 (Figure 2) included coagulation and filtration. 

Chlorine was applied to the raw, settled, and filtered waters. Ammonia was added to the finished 
water to form chloramines. 

Plant 2 was sampled at the following locations: 

(1) filter influent (settled water) or filter effluent 

(2) the effluent of the treated water tank 

(3) the finished water 

In addition, finished water was collected from both plants, and simulated distribution system 
(SDS) testing conducted for average and maximum detention times for that time of the year 
(Table 1). Furthermore, the distribution system was sampled at two locations, one representing 
an average detention time and the other representing a maximum detention time. (Raw water 
was not sampled at plant 2, as it was the same as was used at plant 1.) 


Table L SDS holding times (hr) at the EPA Region 9 treatment plants 


Sample 

10/30/00 

1/23/01 

7/17/01 

3/19/02 

Plant 1 average detention time 

18 

23 

6 

65 

Plant 1 maximum detention time 

NS a 

48 

28 

70 

Plant 2 average detention time 

18 

22 

4 

5 

Plant 2 maximum detention time 

NS 

38 

5 

10 


a NS = Not sampled 


22 












Figure 1 

Plant 1 Schematic 

Alum/ Ferric Chloride 



Reservoir 


Figure 2 

Plant 2 Schematic 


Chlorine 

Alum 



23 


Clearwell 






















































On the day of sampling, information was collected on the operations at each plant 
(Tables 2-3). 


Table 2. Operational information at plant 1 


Parameter 

10/30/00 

1/23/01 

7/17/01 

3/19/02 

Plant flow (mgd) 

11.0 

16.2 

22.0 

15.8 

Ozone dose (mg/L) 

1.84 

2.53 

2.43 

2.33 

HRT 3 in ozone contactor (min) 

4.9 

9.5 

6 

9.8 

CT achieved from ozonation (mg/L-min) 

1.67 

1.24 

0.20 

3.6 

Giardia inactivation achieved from ozonation (logs) 

0.75 

2.82 

1.31 

NA C 

Coagulant dose (mg/L) 

14 

13 

18 

16 

Filter loading rate (gpm/sq ft) 

2.8 

3.4 

4.7 

4.8 

Filter EBCT 1 (min) 

6.7 

7.7 

5.5 

9 

Chlorine dose at ozone contactor effluent (mg/L) 

0 

0 

0 

0 

Chlorine dose at filter effluent (mg/L) 

2.93 

4.65 

2.15 

3.6 

Ammonia dose at clearwell effluent (mg/L as N) 

0.56 

0.72 

0.48 

0.55 


a Hydraulic retention time in cells 1 and 2 only 
b Ferric chloride (FeCh) 

C NA = Not available 

d Empty bed contact time through both media layers 


Table 3. Operational information at plant 2 


Parameter 

10/30/00 

1/23/01 

7/17/01 

3/19/02 

Plant flow (mgd) 

6.8 

5.6 

7.7 

4.4 

Coagulant 3 dose (mg/L) 

20 

19 

25 

12 

Chlorine dose at plant influent (mg/L) 

1.11 

1.3 

1.5 

1.2 

Chlorine dose at filter influent (mg/L) 

0.65 

0.60 

0.8 

0.75 

Chlorine dose at filter effluent (mg/L) 

1.93 

2.31 

1.95 

3.7 

Ammonia dose at effluent of treated water tank 
(mg/L as N) 

0.46 

0.44 

0.5 

0.62 


a Alum [A1 2 ( 804)3 I 4 H 2 O] on 10/30/00 and 1/23/01, ferric chloride (FeCb) on 7/17/01 and 
3/19/02 


Water Quality 

On the day of sampling, information was also collected on the water quality at each plant 
(Tables 4-5). 


24 






























Table 4. Water quality information at plant 1 



PH 

Temperature (°C) 

Disinfectant Residual 3 (mg/L) 

Location 

10/30/00 

1/23/01 

7/17/01 

3/19/02 

10/30/00 

1/23/01 

7/17/01 

3/19/02 

10/30/00 

1/23/01 

7/17/01 

3/19/02 

Raw 

8.16 

8.3 

7.7 

9.07 

17.3 

10.6 

20.7 

13.6 

— 

— 

— 

— 

0 3 eff. 

8.13 

7.89 

7.4 

7.14 

17 

10.4 

22.3 

13.4 

0.34 

0.26 

0.20 

0.37 

Filt. inf. 

7.73 

7.20 

6.8 

6.78 

17.3 

10.9 

21.5 

13.8 

— 

— 

— 

— 

Fill. eff. 

7.84 

6.90 

6.7 

6.82 

17.1 

10.6 

21.0 

13.9 

— 

— 

— 

— 

Clear, eff. 

7.59 

9.0 

6.7 

6.73 

17 

10.5 

21.4 

13.7 

2.26 

3.61 

2.05 

2.64 

Fin. water 

8.20 

8.63 

8.7 

8.22 

16 

9.7 

20.7 

13.2 

1.81 

3.65 

1.86 

2.81 

DS7ave. 

8.1 

8.74 

8.2 

8.54 

17.1 

11.9 

22.3 

14.7 

1.61 

1.62 

1.81 

>2.20 

D S/max 

8.35 

8.65 

8.3 

8.61 

17.9 

11.8 

21.8 

14.4 

1.14 

0.26 

1.78 

>2.20 

SDS/ave. 

8.19 

8.09 

8.6 

8.43 

15.6 

12.4 

21.3 

14.2 

1.67 

1.59 

1.86 

2.11 

SDS/max 

NS 

8.57 

8.2 

8.34 

NS 

10.2 

20.8 

14.9 

NS 

1.21 

1.80 

2.08 


Ozone residuals (values shown in bold) in effluent of cell 2 of ozone contactor; chlorine residuals (values shown in italics) at clearwell effluent; 
chloramine residuals at other locations. 
b DS = Distribution system 


Table 5. Water quality information at plant 2 



PH 

Temperature (°C) 

Disinfectant Residual 3 (mg/L) 

Location 

10/30/00 

1/23/01 

7/17/01 

3/19/02 

10/30/00 

1/23/01 

7/17/01 

3/19/02 

10/30/00 

1/23/01 

7/17/01 

3/19/02 

Filt. eff. D 

7.5 

7.4 

6.7 

7.35 

17.8 

10.7 

21.5 

13.0 

0.72 

0.33 

0.22 

0.26 

Treat, tank' 

7.5 

7.3 

6.6 

7.21 

16.4 

11.5 

21.8 

13.2 

1.69 

1.83 

1.91 

2.71 

Fin. water 

7.88 

8.3 

8.6 

8.74 

16.3 

11.6 

21.7 

13.4 

1.85 

1.88 

1.84 

2.43 

DS/ave. 

8.23 

8.95 

8.5 

8.98 

14.6 

10.9 

21.4 

13.5 

1.38 

1.35 

2.00 

1.83 

DS/max 

8.35 

8.69 

8.5 

8.72 

19.6 

12.4 

21.8 

14.0 

0.96 

0.97 

1.78 

1.92 

SDS/ave. 

8.16 

8.51 

8.14 

8.56 

17.6 

11.4 

21.2 

14.3 

1.55 

1.46 

1.93 

2.13 

SDS/max 

NS 

8.51 

8.10 

8.67 

NS 

10.1 

20.9 

16.1 

NS 

1.50 

2.05 

2.20 


a Chlorine residuals (values shown in italics) at filter effluent and at effluent of treated water tank; chloramine residuals at other locations. 
b Sampled settled water (filter influent) rather than filter effluent on 10/30/00 


'Effluent of treated water tank 


25 















































Other data collected included total organic carbon (TOC) and ultraviolet (UV) 
absorbance (Table 6). The TOC ranged from 3.0 to 4.5 mg/L and the UV was 0.076 to 0.136 
cm* 1 . Typically, ozonation had little effect on TOC. In July 2001, ozonation resulted in a slight 
increase in the value of the TOC. This phenomenon is due to the conversion of “recalcitrant” 

TOC by ozone to a form that can be more readily measured by a TOC analyzer. On the other 
hand, a significant portion of the UV absorbance was reduced by ozone. At plant 1, coagulation 
removed 27-47 % of the TOC and biofiltration removed another 14-21 %. In addition, 
coagulation reduced the UV by 38-63 %. The overall (cumulative) removal of TOC at plant 1 
was 37-53 % and the UV reduction was 70-81 %. At plant 2, 8-47 % of the TOC was removed 
and UV reduced by 51-80 % by the coagulation/filtration process. 


Table 6. TOC and UV removal at the EPA Region 9 treatment plants 


Location 

TOC 

(mg/L) 

UV 

(cm* 1 ) 

SUVA 3 

(L/mg-m) 

Removal/Unit (%) 

Removal/Cumulative (%) 

TOC 

UV 

TOC 

UV 

10/30/2000 








Plant 1 Raw 

3.1 

0.076 

2.4 

— 

— 

— 

— 

Plant 1 03 Eff. 

3.1 

0.039 

1.3 

1.3% 

49% 

1.3% 

49% 

Plant 1 Filter Inf. 

2.3 

0.024 

1.1 

27% 

38% 

27% 

68% 

Plant 1 Filter Eff. 

2.0 

0.023 

1.2 

14% 

4.2% 

37% 

70% 

Plant 2 Filt. Eff. 

2.9 

0.037 

1.3 

7.7% 

51% 

7.7% 

51% 

1/23/2001 








Plant 1 Raw 

4.48 

0.136 

3.0 

— 

— 

— 

— 

Plant 1 03 Eff. 

4.34 

0.070 

1.6 

3.1% 

49% 

3.1% 

49% 

Plant 1 Filter Inf. 

3.11 

0.031 

1.0 

28% 

56% 

31% 

77% 

Plant 1 Filter Eff. 

2.47 

0.031 

1.3 

21% 

0% 

45% 

77% 

Plant 2 Filt. Eff. 

3.00 

0.055 

1.8 

33% 

60% 

33% 

60% 

7/17/2001 








Plant 1 Raw 

2.99 

0.093 

3.1 

— 

— 

— 

— 

Plant 1 03 Eff. 

3.11 

0.048 

1.5 

-4.0% 

48% 

-4.0% 

48% 

Plant 1 Filter Inf. 

1.64 

0.018 

1.1 

47% 

63% 

45% 

81% 

Plant 1 Filter Eff. 

1.4 

0.018 

1.3 

15% 

0% 

53% 

81% 

Plant 2 Filt. Eff. 

1.57 

0.019 

1.2 

47% 

80% 

47% 

80% 

3/19/2002 








Plant 1 Raw 

4.5 

0.132 

2.9 

— 

— 

— 

— 

Plant 1 03 Eff. 

4.4 

0.069 

1.6 

2.2% 

48% 

2.2% 

48% 

Plant 1 Filter Inf. 

2.69 

0.030 

1.1 

39% 

57% 

40% 

77% 

Plant 1 Filter Eff. 

2.2 

0.029 

1.3 

18% 

3.3% 

51% 

78% 

Plant 2 Filt. Eff. 

3.02 

0.060 

2.0 

33% 

55% 

33% 

55% 


a SUVA = Specific ultraviolet absorbance = 100*UV/DOC, 
where DOC = dissolved organic carbon, which typically = 90-95% TOC 
(used TOC values in calculating SUVA) 


Table 7 shows the values of miscellaneous other water quality parameters in the EPA 
Region 9 treatment plants’ raw source water. Bromide ranged from 0.12 to 0.40 mg/L. At both 
plant 1 and plant 2, they treated surface water impacted by saltwater intrusion. 


26 




































Table 7. Miscellaneous water quality parameters in plant 1 and 2’s raw water 


Date 

Bromide 

(mg/L) 

Alkalinity 

(mg/L) 

Ammonia 
(mg/L as N) 

10/30/2000 

0.16 

106 

ND a 

01/23/2001 

0.40 

66 

0.04 

07/17/2001 

0.14 

72 

0.04 

03/19/2002 

0.12 

82 

ND 


a ND = Not detected 


The source water was moderate in alkalinity. The raw-water pH varied from 7.7 to 9.1 
(Table 4). The source water can have significant variability in these inorganic parameters. 

DBPs 


Oxyhalides. Ozonation resulted in the formation of <3 to 26 pg/L of bromate (Table 8). 
Bromate formation was highest in January 2001 when the bromide concentration in the raw 
water was highest (Table 7). 

Table 8. Oxyhalide formation at the EPA Region 9 treatment plants 


Location 

Bromate 

(uo/L) 

Chlorate 

(uq/L) 

Bromate/Bromide 

(umol/umol) 

10/30/2000 




Plant 1 03 eff. 

5.7 

10 

2.2% 

Plant 1 clear, eff. 

5.2 

157 


1/23/2001 




Plant 1 03 eff. 

26 

5.9 

4.0% 

Plant 1 clear, eff. 

22 

121 


Plant 2 fin. water 

ND 

114 


7/17/2001 




Plant 1 03 eff. 

4.9 

9.8 

2.2% 

Plant 1 clear, eff. 

5.5 

133 


Plant 2 fin. water 

ND 

93 


3/19/2002 




Plant 1 03 eff. 

ND a (2) 

10 

1.0% 

Plant 1 clear, eff. 

4 

80 

2.1% 

Plant 2 fin. water 

ND (1) 

127 



a ND = Not detected 

(bromate minimum reporting level [MRL] = 3 |jg/L; 
value in parenthesis is < MRL) 


The conversion of bromide to bromate was 1-4 % (on a molar basis), which is a typical 
conversion rate for an ozone plant operating for Giardia inactivation (Douville and Amy, 2000). 
In addition, sodium hypochlorite can be contaminated with low or sub-pg/L levels of bromate 
(Delcomyn et al., 2000). In March 2002, there was an increase in the concentration of bromate 
in the treated water at plant 1 after secondary disinfection (4 versus <3 pg/L). Bromate was not 
detected (minimum reporting level of 3 pg/L) at plant 2. However, some chlorate was 


27 





























introduced into the finished waters at both plants from secondary disinfection (Table 8) (chlorate 
is a by-product formed during the decomposition of the hypochlorite stock solution [Bolyard et 
al. [1992]). 

Biodegradable Organic Matter. Ozone can convert natural organic matter in water to 
carboxylic acids (Kuo et al., 1996) and other assimilable organic carbon (AOC) (van der Kooij et 
al., 1982). Table 9 shows the carboxylic acid and AOC data for plant 1. Because AOC data are 
expressed in units of micrograms of carbon per liter (pg C/L), the carboxylic acid data were 
converted to the same units. A portion of the molecular weight (MW) of each carboxylic acid is 
due to carbon atoms (i.e., 27-49 %) and the remainder is due to oxygen and hydrogen atoms. 

The sums of the five carboxylic acids (on a pg C/L basis) were compared to the AOC data. On a 
median basis for each sample date, 19 to 30 % of the AOC was accounted for by the carboxylic 
acids. 


Figures 3 and 4 show the AOC and the carboxylic acid results, respectively, for the July 
2001 sample date. Ozonation resulted in a significant increase in AOC and the concentration of 
the carboxylic acids, especially oxalate. (Note, one of the bacterial strains used in the AOC 
method [i.e., Spirillum NOX] is used to estimate oxalate-carbon equivalents of the AOC [van der 
Kooij and Hijnen, 1984].) The carboxylic acids and AOC were both significantly reduced in 
concentration in the downstream treatment processes (coagulation/sedimentation) prior to 
biological filtration. Because chlorine was not applied until after the filters, there may have been 
biological activity in the basins that degraded the AOC. Also, some of the AOC may have been 
removed by the coagulation process (Volk and LeChevallier, 2002) along with the TOC 
(Table 6). 

Figures 5 and 6 show the formation and removal of AOC and oxalate, respectively, for all 
of the sample dates. AOC increased from 16-83 pg C/L in the raw water to 504-707 pg C/L in 
the ozonated water. AOC decreased to 148-333 pg C/L in the settled water and to 131- 
224 pg C/L in the filtered water. Oxalate increased from 14-18 pg/L in the raw water to 314- 
409 pg/L in the ozonated water. Oxalate decreased to 56-223 pg/L in the settled water and to 9- 
33 pg/L in the filtered water. The formation and removal of carboxylic acids—in particular that 
of oxalate—and AOC tended to follow the same trends through the different treatment processes. 

Halogenated Organic and Other Non-halogenated Organic DBPs. Tables 10 and 11 
(10/30/00), Tables 13 and 14 (1/23/01), Tables 16 and 17 (7/17/01), and Tables 20 and 21 
(3/19/02) show results for the halogenated organic DBPs that were analyzed by MWDSC. 


28 


Table 9. Formation and removal of carboxylic acids and AOC at plant 1 


Location 

Concentration 3 (pg/L) 

Concentration (pg C/L) 

Sum/ 

AOC 

Acetate 

Propionate 

Formate 

Pyruvate 

Oxalate 

Acetate 

Propionate 

Formate 

Pyruvate 

Oxalate 

Sum 

AOC-P17 

AOC-NOX 

AOC 

10/30/2000 
















Raw water 

NO 

ND 

ND 

ND 

17 

ND 

ND 

ND 

ND 

4.6 

4.6 

N/A b 

N/A 



Ozone effluent 

NO 

ND 

ND 

ND 

314 

ND 

ND 

ND 

ND 

86 

86 

168 

336 

504 

17% 

Filter influent 

ND 

ND 

32 

19 

70 

ND 

ND 

8.6 

7.8 

19 

36 

N/A 

N/A 



Filter effluent 

ND 

ND 

25 

25 

33 

ND 

ND 

6.6 

10 

9.0 

25 

72 

101 

123 

21% 














median 

19% 

1/23/2001 
















Raw water 

N/A 

N/A 

N/A 

N/A 

N/A 







13 

3.4 

16 


Ozone effluent 

N/A 

N/A 

N/A 

N/A 

N/A 







191 

386 

§7? 


Filter influent 

N/A 

N/A 

N/A 

N/A 

N/A 







54 

279 

333 


Filter effluent 

N/A 

N/A 

N/A 

N/A 

N/A 







50 

91 

141 


7/17/2001 
















Raw water 

13 

ND 

15 

13 

14 

5.3 

ND 

3.9 

5.5 

3.9 

19 

54 

29 

83 

22% 

Ozone effluent 

80 

8.8 

223 

50 

378 

32 

4.4 

60 

21 

103 

220 

186 

516 

703 

31% 

Filter influent 

16 

5.5 

43 

19 

56 

6.4 

2.7 

11 

7.9 

15 

44 

41 

107 

148 

30% 

Filter effluent 

45 

ND 

43 

14 

22 

18 

ND 

12 

5.7 

5.9 

41 

43 

89 

J13L 















median 

30% 

3/19/2002 
















Raw water 

11 

ND 

12 

7.1 

18 

4.3 

ND 

3.2 

2.9 

5.0 

15 

48 

4.7 

53 

29% 

Ozone effluent 

77 

ND 

206 

31 

409 

31 

ND 

55 

13 

112 

211 

266 

441 

707 

30% 

Filter influent 

40 

ND 

125 

23 

223 

16 

ND 

33 

9.5 

61 

120 

38 

205 

243 

49% 

Filter effluent 

ND 

ND 

ND 

4.0 

CO 

-"J 

ND 

ND 

ND 

1.7 

2.4 

4,9 

51 

112 

224 

2% 














median 

29% 

Formula 

CH3COO 

CH3CH2COO 

HCOO' 

CH3COCOO 

C2O4 2 ' 


MW (am/molel 

59 

73 

45 

87 

88 

C portion (am/mole) 

24 

36 

12 

36 

24 

C% of MW 

41% 

49% 

27% 

41% 

27% 


a Method detection limit (MDL) = 3 pg/L; reporting detection level (RDL) = 15 pg/L; value in italics < RDL 


29 



















































Carboxylic Acids (|jg/L) Total AOC (pg C/L) 


Figure 3 


Formation and Removal of AOC at Plant 1: 7/17/01 


■ AOC-P17 DAOC-NOX 



Figure 4 


800 

700 - 

600 

500 

400 - 

300 - 

200 - 

100 

0 


Formation and Removal of Carboxylic Acids at Plant 1: 7/17/01 


□ Acetate □ Propionate 11 Formate ■ Pyruvate □ Oxalate 



30 



















































































Figure 5 


Formation and Removal of AOC at Plant 1 


110/30/2000 □ 1/23/2001 H7/17/2001 D3/19/2002 


800 



Raw water 


Ozone effluent 


Filter influent 


Filter effluent 


Figure 6 


Formation and Removal of Oxalate at Plant 1 


■ 10/30/2000 ■ 7/17/2001 D3/19/2002 



31 
































































































Table 10. DBP results at plant 1 (10/30/00) 


10/30/2000 

MRL a 

Plant 1 b 

Compound 

mq/l 

Raw 

0 3 Eff 

Clear. Eff 

Fin. Water 

SDS 

DS/Ave. 

DS/Max. 

Halomethanes 









Chloromethane 

0.15 

ND d 

ND 

ND 

ND 

ND 

ND 


Bromomethane 

0.20 

ND 

ND 

ND 

ND 

ND 

ND 


Bromochloromethane 

0.14 

ND 

ND 

ND 

ND 

ND 

ND 


Dibromomethane 

0.11 

ND 

ND 

ND 

ND 

ND 

ND 


Chloroform 6 

0.1 

ND 

0.7 

1 

1 

2 

8 

4 

Bromodichloromethane 6 

0.1 

ND 

0.7 

1 

3 

3 

3 

4 

Dibromochloromethane 6 

0.19 

ND 

1 

4 

8 

8 

7 

11 

Bromoform 6 

0.14 

ND 

0.2 

2 

4 

4 

3 

5 

THM4 f 


ND 

3 

8 

16 

17 

21 

24 

Dichloroiodomethane 

0.5 

ND 

ND 

NR 9 

NR 

1 

1 

NR 

Bromochloroiodomethane 

0.5 

ND 

NR 

NR 

NR 

NR 

NR 

NR 

Dibromoiodomethane 

0.5 

ND 

ND 

ND 

NR 

NR 

NR 

NR 

Chlorodiiodomethane 

0.59 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.53 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.22 

ND 

NR 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 

ND 

ND 

ND 

ND 

ND 

ND 


T ribromochloromethane 

0.1 

ND 

ND 

ND 

0.1 

0.1 

ND 

0.1 

Haloacetic acids 









Monochloroacetic acid 6 

2 



ND 

ND 

ND 

ND 


Monobromoacetic acid 6 

1 



ND 

ND 

ND 

ND 


Dichloroacetic acid 6 

1 



ND 

1.3 

1.8 

5.8 


Bromochloroacetic acid 6 

1 



ND 

1.6 

2.0 

2.2 


Dibromoacetic acid 6 

1 



ND 

2.1 

2.9 

2.1 


Trichloroacetic acid 6 

1 



ND 

ND 

ND 

1.8 


Bromodichloroacetic acid 

1 



ND 

ND 

ND 

ND 


Dibromochloroacetic acid 

1 



ND 

ND 

ND 

ND 


Tribromoacetic acid 

2 



ND 

ND 

ND 

ND 


HAA5 h 




ND 

3.4 

4.7 

10 


HAA9' 




ND 

5.0 

6.7 

12 


DXAA j 




ND 

5.0 

6.7 

10 


TXAA k 




ND 

ND 

ND 

1.8 


Haloacetonitriles 









Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile 6 

0.1 

ND 

ND 

ND 

0.2 

0.2 

0.4 

0.3 

Bromochloroacetonitrile 6 

0.1 

ND 

ND 

0.2 

0.4 

0.4 

0.4 

0.6 

Dibromoacetonitrile 6 

0.11 

ND 

ND 

0.3 

0.6 

0.6 

0.4 

0.7 

T richloroacetonitrile 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetaldehvdes 









Dichloroacetaldehvde 

0.16 

ND 

ND 

ND 

0.4 

0.7 

0.4 

0.7 

Bromochloroacetaldebyde 1 

Chloral hydrate 6 

0.2 

ND 

ND 

ND 

1 

2 

2 

0.6 

T ribromoacetaldehyde 

0.1 

0.2 

ND 

0.2 

0.1 

ND 

ND 

0.2 


32 





























































Table 10 (continued) 


10/30/2000 

MRL a 

Plant 1 b 

Compound 

mq/l 

Raw 

O 

Ca> 

m 

Clear. Eff 

Fin. Water 

SDS 

DS/Ave. 

DS/Max. 

Haloketones 









Chloropropanone 

0.1 

ND 

ND 

ND 

0.2 

0.3 

ND 

0.2 

1,1 -Dichloropropanone 6 

0.1 

ND 

ND 

ND 

ND 

0.2 

ND 

0.2 

1,3-DichloroDroDanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromoorooanone 

3 

ND 

ND 

ND 

ND 

ND 

ND 


1,1,1-Trichloropropanone e 

0.1 

ND 

ND 

ND 

ND 

ND 

0.2 

0.1 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

0.1 

1 -Bromo-1,1 -dichloropropanone 

3 

ND 

ND 

ND 

ND 

ND 

ND 


1,1,1 -T ribromoorooanone 

3 

ND 

ND 

ND 

ND 

ND 

ND 


1.1,3-T ribromoorooanone 

3 

ND 

ND 

ND 

ND 

ND 

ND 


1,1.3,3-TetrachloroDrooanone 

0.1 

ND 

ND 

1 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrabromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 









Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

3 

ND 

ND 

ND 

ND 

ND 

ND 


Dibromonitromethane 

0.11 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 6 

0.1 

ND 

ND 

ND 

0.2 

0.3 

0.2 

0.2 

Miscellaneous Comnounds 









Methyl ethyl ketone 

1.9 

ND 

ND 

ND 

ND 

ND 

ND 


Methyl tertiary butyl ether 

0.16 

0.9 

0.6 

0.6 

0.8 

0.7 

0.4 


Benzyl chloride 

0.5-3 

ND 

ND 

ND 

NR 

NR 

NR 

NR 


a MRL = Minimum reporting level, which equals method detection limit (MDL) 
or lowest calibration standard or concentration of blank 

b Plant 1 sampled at (1) raw water, (2) ozone contactor effluent, (3) clearwell effluent, 

(4) finished water, (5) SDS testing of finished water, 

(6) distribution system at average detention time and (7) at maximum detention time. 
c Plant 2 sampled at (1) filter influent, (2) effluent of treated water tank, 

(3) finished water, (4) SDS testing of finished water, 

(5) distribution system at average detention time and (6) at maximum detention time. 
d ND = Not detected at or above MRL 

e DBP in the Information Collection Rule (ICR) (note: some utilities collected data for all 9 
haloacetic acids for the ICR, but monitoring for only 6 haloacetic acids was required) 
f THM4 = Sum of 4 THMs (chloroform, bromodichloromethane, dibromochloromethane, bromoform) 
S NR = Not reported, due to interference problem on gas chromatograph or 
to problem with quality assurance 

h HAA5 = Sum of 5 haloacetic acids (monochloro-, monobromo-, dichloro-, dibromo-, 
trichloroacetic acid) 

'HAA9 = Sum of 9 haloacetic acids 

j DXAA = Sum of dihaloacetic acids (dichloro-, bromochloro-, dibromoacetic acid) 

k TXAA = Sum of trihaloacetic acids (trichloro-, bromodichloro-, dibromochoro-, tribromoacetic acid) 

'Bromochloroacetaldehyde and chloral hydrate co-eulte; result = sum of 2 DBPs 

m <3: Concentration less than MRL of 3 pg/L 


33 





































Table 11. DBP results at plant 2 (10/30/00) 


10/30/2000 

MRL a 

Plant 2 C 

Compound 

mq/l 

Filt. Inf 

Treat. Tank 

Fin. Water 

SDS 

DS/Ave. 

DS/Max. 

Halomethanes 








Chloromethane 

0.15 


ND 

ND 

ND 

ND 


Bromomethane 

0.20 


ND 

ND 

ND 

ND 


Bromochloromethane 

0.14 


ND 

ND 

ND 

ND 


Dibromomethane 

0.11 


ND 

ND 

ND 

ND 


Chloroform 6 

0.1 

10 

11 

14 

15 

14 

17 

Bromodichloromethane 6 

0.1 

8 

15 

14 

17 

23 

20 

Dibromochloromethane 6 

0.19 

16 

25 

25 

26 

35 

31 

Bromoform 6 

0.14 

4 

5 

5 

5 

6 

6 

THM4 f 


38 

56 

58 

63 

78 

74 

Dichloroiodomethane 

0.5 

NR 

NR 

NR 

3 

4 

NR 

Bromochloroiodomethane 

0.5 

NR 

1 

1 

1 

1 

NR 

Dibromoiodomethane 

0.5 

NR 

NR 

NR 

NR 

1 

NR 

Chlorodiiodomethane 

0.59 

ND 

ND 

ND 

ND 

0.7 

ND 

Bromodiiodomethane 

0.53 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.22 

NR 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 


ND 

ND 

ND 

ND 


T ribromochloromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 








Monochloroacetic acid 6 

2 


ND 

ND 

ND 

ND 


Monobromoacetic acid 6 

1 


ND 

ND 

ND 

ND 


Dichloroacetic acid 6 

1 


9.9 

9.5 

11 

11 


Bromochloroacetic acid 6 

1 


9.4 

9.1 

10 

11 


Dibromoacetic acid 6 

1 


6.9 

6.6 

7.1 

8.1 


Trichloroacetic acid 6 

1 


8.4 

7.9 

8.6 

8.4 


Bromodichloroacetic acid 

1 


6.0 

5.6 

3.4 

ND 


Dibromochloroacetic acid 

1 


2.5 

2.4 

1.6 

ND 


Tribromoacetic acid 

2 


ND 

ND 

ND 

ND 


HAA5 h 



25 

24 

27 

28 


HAA9' 



43 

41 

42 

39 


DXAA j 



26 

25 

28 

30 


TXAA k 



17 

16 

14 

8.4 


Haloacetonitriles 








Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile 6 

0.1 

1 

2 

2 

2 

2 

2 

Bromochloroacetonitrile 6 

0.1 

1 

2 

2 

2 

2 

2 

Dibromoacetonitrile 6 

0.11 

0.8 

1 

1 

1 

2 

1 

T richloroacetonitrile 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetaldehvdes 








Dichloroacetaldehyde 

0.16 

0.6 

0.9 

1 

2 

1 

2 

Bromochloroacetaldehyde 1 
Chloral hydrate 6 

0.2 

3 

4 

4 

4 

4 

5 

T ribromoacetaldehyde 

0.1 

0.5 

0.6 

0.4 

ND 

0.3 

ND 


34 






























































Table 11 (continued) 


10/30/2000 

MRL a 

Plant 2 C 

Compound 

pg/L 

Filt. Inf 

Treat. Tank 

Fin. Water 

SDS 

DS/Ave. 

DS/Max. 

Haloketones 








Chloropropanone 

0.1 

ND 

ND 

ND 

0.1 

0.2 

0.2 

1,1-Dichloropropanone e 

0.1 

0.4 

0.3 

0.3 

0.4 

0.4 

0.4 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

3 


ND 

ND 

ND 

ND 


1,1,1 -T richloropropanone 6 

0.1 

0.9 

2 

1 

0.7 

1 

0.3 

1,1,3-Trichloropropanone 

0.1 

0.1 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1.1 -dichloropropanone 

3 


<3 m 

<3 

ND 

ND 


1,1,1-Tribromopropanone 

3 


ND 

ND 

ND 

ND 


1,1,3-T ribromopropanone 

3 


ND 

ND 

ND 

ND 


1,1,3,3-Tetrachloropropanone 

0.1 

0.2 

0.2 

0.2 

0.1 

0.2 

ND 

1,1,3,3-Tetrabromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 








Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

3 


ND 

ND 

ND 

ND 


Dibromonitromethane 

0.11 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 6 

0.1 

ND 

ND 

ND 

0.2 

0.2 

0.3 

Miscellaneous Compounds 








Methyl ethyl ketone 

1.9 


ND 

ND 

ND 

ND 


Methyl tertiary butyl ether 

0.16 


0.9 

0.9 

0.9 

0.9 


Benzyl chloride 

0.5-3 

NR 

NR 

NR 

NR 

NR 

NR 


35 



































Table 12. Additional target DBP results (pg/L) at the EPA Region 9 treatment plants 
(10/30/00) 


10/30/00 

Plant l a 

Plant 2 b 

Compound 

Raw 

OE 

FE 

PE 

DS 

Raw 

FI 

TT 

PE 

DS 

Monochloroacetaldehyde 

0 

0 

0 

0 

0 

0 

0.1 

0.1 

0.1 

0.2 

Dichloroacetaldehyde 

0 

0 

0 

0.6 

0.7 

0 

0.9 

1.1 

1.4 

1.7 

Bromochloroacetaldehyde 

0 

0 

0 

1.0 

1.3 

0 

1.7 

1.9 

1.3 

1.1 

3,3-Dichloropropenoic acid 

0 

0 

0 

0.1 

0.1 


0.3 

0.4 

0.7 

0.2 

Bromochloromethylacetate 

0.5 

0.1 

0.1 

0.1 

0.1 


0 

0 

0 

0 

2,2-Dichloroacetamide 

0 

0 

0 

0.2 

0.3 


0 

0 

0.8 

1.4 

TOX (|ig/L as Cl ) 

NA C 

NA 

10.2 

75.5 

109 


NA 

NA 

199 

135 

Cyanoformaldehyde 

<0.1 

<0.1 

<0.1 

0.2 

0.2 


0.1 

<0.1 

0.3 

0.3 

5-Keto-l-hexanal 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 


<0.4 

<0.4 

<0.4 

<0.4 

6-Hydroxy-2-hexanone 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 


<0.4 

<0.4 

<0.4 

<0.4 

Dimethylglyoxal 

<0.4 

1.3 

1.1 

<0.4 

<0.4 


<0.4 

<0.4 

<0.4 

<0.4 

trans- 2-Hexenal 

<0.5 

<0.5 

<0.5 

<0.5 

<0.5 


<0.5 

<0.5 

<0.5 

<0.5 


a Plant 1 sampled at (1) raw water, (2) ozone contactor effluent (OE), (3) filter effluent (FE), (4) 
finished water at plant effluent (PE), and (5) distribution system (DS) at average detention time. 
b Plant 2 sampled at (1) filter influent (FI), (2) effluent of treated water tank (TT), (3) finished 
water at PE, and (4) DS at average detention time. 

C NA = Not available 


36 



























Table 13. DBP results at plant 1 (1/23/01) 


1/23/2001 

MRL a 

mq/l 

Plant 1 n 

Compound 

Raw 

0 3 Eff 

Clear. Eff 

Fin. Water 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Halomethanes 










Chloromethane 

0.15 

ND d 

ND 

ND 

ND 

ND 


ND 


Bromomethane 

0.20 

ND 

ND 

ND 

ND 

ND 


ND 


Bromochloromethane 

0.14 

ND 

ND 

ND 

ND 

ND 


ND 


Dibromomethane 

0.11 

ND 

ND 

ND 

ND 

ND 


ND 


Chloroform® 

0.1 

ND 

0.2 

0.5 

NR 9 

2 

NR 

1 

NR 

Bromodichloromethane 6 

0.1 

ND 

1 

2 

NR 

7 

NR 

6 

NR 

Dibromochloromethane 6 

0.12 

ND 

1 

4 

NR 

16 

NR 

20 

NR 

Bromoform® 

0.12 

ND 

0.5 

3 

NR 

20 

NR 

30 

NR 

THM4 f 


ND 

3 

10 

NR 

45 

NR 

57 

NR 

Dichloroiodomethane 

0.25 

ND 

ND 

ND 

0.2 

0.3 

NR 

0.2 

NR 

Bromochloroiodomethane 

0,20 

(sip 

ND 

ND 

ND 

0.2 

NR 

ND 

NR 

Dibromoiodomethane 

0.64 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.60 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.70 

ND 

1 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 

ND 

ND 

ND 

ND 

ND 


ND 


Haloacetic acids 










Monochloroacetic acid 6 

2 



ND 

ND 

ND 


ND 


Monobromoacetic acid 6 

1 



1.1 

1.4 

1.2 


1.4 


Dichloroacetic acid 6 

1 



2.1 

2.0 

3.6 


2.4 


Bromochloroacetic acid 6 

1 



3.0 

3.0 

7.0 


4.9 


Dibromoacetic acid® 

1 



14 

13 

13 


11 


Trichloroacetic acid 6 

1 



ND 

ND 

1.0 


ND 


Bromodichloroacetic acid 

1 



1.0 

ND 

1.4 


ND 


Dibromochloroacetic acid 

1 



2.2 

1.4 

2.1 


1.4 


Tribromoacetic acid 

2 



ND 

ND 

ND 


ND 


HAA5 h 




17 

16 

19 


15 


HAA9' 




23 

21 

29 


21 


DXAA j 




19 

18 

24 


18 


TXAA k 




3.2 

1.4 

4.5 


1.4 


Haloacetonitriles 










Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile 6 

0.1 

ND 

ND 

0.1 

0.1 

0.2 

0.4 

0.2 

0.2 

Bromochloroacetonitrile® 

0.1 

ND 

ND 

0.3 

0.3 

0.3 

1 

0.9 

0.9 

Dibromoacetonitrile 6 

0.10 

ND 

ND 

0.6 

0.7 

0.7 

2 

2 

2 

T richloroacetonitrile 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetaldehvdes 










Dichloroacetaldehvde 

0.16 

ND 

0.3 

0.8 

NR 

0.8 

1 

2 

2 

Bromochloroacetaldehvde 

0.1 

ND 

0.6 

3 

3 

3 

6 

7 

6 

Chloral hydrate® 

0.1 

ND 

0.2 

0.1 

NR 

0.2 

0.3 

0.2 

0.2 

T ribromoacetaldehyde 

0.1 

ND 

0.1 

1 

NR 

0.5 

0.4 

0.2 

ND 


37 




























































Table 13 (continued) 


1/23/2001 

MRL 

fjg/L 

Plant 1 

Compound 

Raw 

0 3 Eff 

Clear. Eff 

Fin. Water 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Haloketones 










Chloropropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dichloropropanone e 

0.10 

ND 

0.2 

0.3 

0.2 

0.3 

0.2 

0.1 

0.2 

1.3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

N/A p 

NR 


NR 

NR 

NR 


NR 


1.1,1-TrichloroDroDanone e 

0.10 

ND 

ND 

0.2 

0.3 

0.2 

0.2 

0.2 

ND 

1.1,3-TrichloroDrooanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

N/A 

NR 


NR 

NR 

NR 


NR 


1,1,1 -T ribromopropanone 

N/A 

NR 


NR 

NR 

NR 


NR 


1,1,3-T ribromopropanone 

N/A 

NR 


NR 

NR 

NR 


NR 


1,1,3,3-Tetrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1.1,3-TetrachloroDroDanone 

N/A 

NR 


NR 

NR 

NR 


NR 


1,1,3,3-Tetrabromopropanone 

0.5 

ND 

ND 

0.2-0.6 q 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 










Bromonitromethane 

0.1 

ND 

ND 

0.1 

0.1 

0.1 

0.2 

0.2 

0.2 

Dichloronitromethane 

N/A 

NR 


NR 

NR 

NR 


NR 


Bromochloronitromethane 

N/A 

NR 


NR 

NR 

NR 


NR 


Dibromonitromethane 

0.10 

ND 

ND 

0.1-0.2 q 

0.1-0.2 

0.1-0.2 

0.2-0.3 

0.1-0.2 

ND 

Chloropicrin 6 

0.1 

ND 

ND 

ND 

ND 

ND 

0.2 

0.2 

0.4 

Miscellaneous ComDounds 










Methvl ethvl ketone 

1,9 

NP 

ND 

ND 

ND 

ND 


ND 


Methyl tertiary butyl ether 

0.16 

0.3 

0.2 

0.2 

0.2 

0.2 


0.2 


Benzyl chloride 

2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


n Plant 1 sampled at (1) raw water, (2) ozone contactor effluent, (3) clearwell effluent, (4) finished water, 

(5) SDS testing of finished water at average detention time and (6) at maximum detention time, and 
(7) distribution system at average detention time and (8) at maximum detention time. 

“Plant 2 sampled at (1) filter effluent, (2) effluent of treated water tank, (3) finished water, 

(4) SDS testing of finished water at average detention time and (5) at maximum detention time, and 

(6) distribution system at average detention time and (7) at maximum detention time. 

P N/A = Not applicable 

q Spike recovery >>100%; range of values represents reported values and values corrected for recovery 


38 








































Table 14. DBP results at plant 2 (1/23/01) 


1/23/2001 

MRL 

mq/l 

Plant 2° 

Compound 

Filt. Eff 

Treat. Tank 

Fin. Water 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

hialomethanes 









Chloromethane 



ND 

ND 

ND 


ND 


Bromomethane 

0.20 


ND 

ND 

ND 


ND 


Bromochloromethane 

0.14 


ND 

ND 

ND 


ND 


Dibromomethane 

0.11 


ND 

ND 

ND 


ND 


Chloroform 6 

0.1 

NR 

8 

11 

18 

NR 

17 

NR 

Bromodichloromethane 6 

0.1 

NR 

20 

30 

40 

NR 

40 

NR 

Dibromochloromethane 6 

0.12 

NR 

30 

40 

50 

NR 

50 

NR 

Bromoform 6 

0.12 

NR 

18 

18 

19 

NR 

20 

NR 

THM4 f 


NR 

76 

99 

127 

NR 

127 

NR 

Dichloroiodomethane 

0.25 

NR 

0.5 

0.6 

0.4 

NR 

0.5 

NR 

Bromochloroiodomethane 

0.20 

NR 

0.6 

0.8 

0.4 

NR 

0.5 

NR 

Dibromoiodomethane 

0.64 

ND 

ND 

0.6 

0.8 

ND 

ND 

0.8 

Chlorodiiodomethane 

0-52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.60 

0.6 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.70 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 


ND 

ND 

ND 


ND 


Haloacetic acids 









Monochloroacetic acid 6 

2 


ND 

ND 

ND 


ND 


Monobromoacetic acid 6 

1 


1.2 

1.2 

1.3 


1.4 


Dichloroacetic acid 6 

1 


14 

14 

15 


15 


Bromochloroacetic acid 6 

1 


19 

18 

19 


19 


Dibromoacetic acid 6 

1 


18 

18 

20 


20 


Trichloroacetic acid 6 

1 


9.7 

8.6 

8.6 


9.1 


Bromodichloroacetic acid 

1 


16 

15 

15 


15 


Dibromochloroacetic acid 

1 


15 

15 

14 


15 


Tribromoacetic acid 

2 


3.9 

3.6 

3.3 


3.5 


HAA5 h 



43 

42 

45 


46 


HAA9' 



97 

93 

96 


98 


DXAA' 



51 

50 

54 


54 


txaa k 



45 

42 

41 


43 


Haloacetonitriles 









Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile 6 

0.1 

2 

2 

2 

2 

2 

2 

2 

Bromochloroacetonitrile 6 

0.1 

2 

3 

3 

3 

3 

3 

3 

Dibromoacetonitrile 6 

0.10 

2 

3 

2 

3 

3 

3 

3 

Trichloroacetonitrile 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetaldehvdes 









Dichloroacetaldehvde 

0.16 

1 

2 

2 

3 

4 

3 

3 

Bromochloroacetaldehvde 

0.1 

4 

4 

4 

4 

3 

4 

4 

Chloral hydrate 6 

0.1 

0.6 

1 

1 

2 

2 

2 

2 

T ribromoacetaldehyde 

0.1 

1 

3 

3 

1 

0.2 

1 

0.5 


39 



























































Table 14 (continued) 


1/23/2001 

MRL 

mq/l 

Plant 2 

Compound 

Filt. Eff 

Treat. Tank 

Fin. Water 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloketones 









Chloropropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dichloropropanone® 

0.10 

0.4 

0.4 

0.4 

0.4 

0.5 

0.6 

0.6 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

N/A 


NR 

NR 

NR 


NR 


1,1,1 -T richloropropanone® 

0.10 

1 

1 

1 

1 

0.7 

1 

1 

1,1,3-T richloropropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

N/A 


NR 

NR 

NR 


NR 


1 ,1,1 -Tribromopropanone 

N/A 


NR 

NR 

NR 


NR 


1,1,3-T ribromopropanone 

N/A 


NR 

NR 

NR 


NR 


1,1,3,3-Tetrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1.1,3-Tetrachloropropanone 

N/A 


NR 

NR 

NR 


NR 


1,1,3,3-Tetrabromopropanone 

0.5 

0.7-2 

0.5-2 

0 .6-2 

0.3-0.9 

ND 

ND 

ND 

Halonitromethanes 









Bromonitromethane 

0.1 

0.2 

0.2 

0.1 

ND 

ND 

ND 

ND 

Dichloronitromethane 

N/A 


NR 

NR 

NR 


NR 


Bromochloronitromethane 

N/A 


NR 

NR 

NR 


NR 


Dibromonitromethane 

0.10 

0 .2-0.4 

0 .2-0.5 

0 .2-0.4 

0 .2-0.3 

<0.1-0.1 

ND 

ND 

Chloropicrin® 

0.1 

0.2 

0.3 

ND 

0.5 

0.8 

1 

2 

Miscellaneous Comoounds 









Methvl ethvl ketone 

1.9 


ND 

ND 

ND 


ND 


Methyl tertiary butyl ether 

0.16 


0.3 

0.3 

0.3 


0.3 


Benzyl chloride 

2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


40 









































Table 15. Occurrence of other DBPs a at plant 1 (1/23/01) 


Compound 

ft 

Halomethanes 

Bromochloromethane 

Dibromomethane 

Bromodichloromethane b 

Dibromochloromethane 

Bromoform 

Dichloroiodomethane 

Bromochloroiodomethane 

Dibromoiodomethane 

OE 

X 

X 

X 

X 

X 

PE 

X 

X 

X 

X 

X 

Haloacids 

Bromoacetic acid 


X 

Dichloroacetic acid 

- 

X 

Bromochloroacetic acid 

X 

X 

Dibromoacetic acid 

X 

X 

Dibromochloroacetic acid 

- 

X 

Tribromoacetic acid 

- 

X 

2,2-Dibromopropanoic acid 

- 

X 

3,3-Dibromopropenoic acid 

- 

X 

cis-2,3-Dibromopropenoic acid 

- 

X 

Tribromopropenoic acid 

- 

X 

2-Bromobutanoic acid 

- 

X 

7ra/7s-4-Bromo-2-butenoic acid 

- 

X 

c/s-4-Bromo-2-butenoic acid 

- 

X 

2,3-Dibromo-2-butenoic acid 

- 

X 

Bromodichloro-butenoic acid c 

- 

X 

Bromochloro-4-oxopentanoic acid 

- 

X 

3,3-Dibromo-4-oxopentanoic acid 

- 

X 

cis-2-Bromo-butenedioic acid 

- 

X 

trans-2,3-Dibromo-butenedioic acid 

- 

X 

cis-2-Bromo-3-methylbutenedioic 

- 

X 

acid 

- 

X 

Haloacetonitriles 

Dichloroacetonitrile 


X 

Bromochloroacetonitrile 

- 

X 

Dibromoacetonitrile 

- 

X 


Compound 

OE 

PE 

Haloaldehydes 

Dichloroacetaldehyde 

X 


Bromochloroacetaldehyde 

X 

X 

Trichloroacetaldehyde 

X 

- 

T ribromoacetaldehyde 

X 

- 

2-Bromo-2-methylpropanal 

- 

X 

Haloketones 

1,1 -Dichloropropanone 

X 

X 

1 -Bromo-1 -chloropropanone 

- 

X 

1,1 -Dibromopropanone 

X 

X 

1,1,1 -Trichloropropanone 

X 

X 

1,1,3-Trichloropropanone 

- 

X 

1 -Bromo-1,1 -dichloropropanone 

- 

X 

1,1,1 -Tribromopropanone 

- 

X 

1,1,3,3-Tetrachloropropanone 

X 

X 

1,1,3-Tribromo-3-chloropropanone 

- 

X 

1,1,3,3-Tetrabromopropanone 

X 

X 

Halonitromethanes 

Bromonitromethane 


X 

Dibromonitromethane 

- 

X 

Miscellaneous Halogenated DBPs 



Chlorobenzene 

X 

X 

Tribromophenol 

- 

X 

Non-halogenated DBPs 



Glyoxal 

X 

X 

Pentanoic acid 

X 

X 

Hexanoic acid 

X 

X 

Heptanoic acid 

X 

X 

Octanoic acid 

X 

X 

Nonanoic acid 

X 

X 

Decanoic acid 

X 

X 

Undecanoic acid 

- 

X 

Dodecanoic acid 

- 

X 

Tetradecanoic acid 

X 

X 

Pentadecanoic acid 

X 

X 

Hexadecanoic acid 

X 

X 

Octadecanoic acid 

X 

X 

Ethanedioic acid 

- 

X 

Octanedioic acid 

- 

X 

Nonanedioic acid 

X 

X 


a DBPs detected by broadscreen gas chromatography/mass spectrometry (GC/MS) technique 
b Compounds listed in italics were confirmed through the analysis of authentic standards; haloacids 
and non-halogenated carboxylic acids identified as their methyl esters. 
c Exact isomer not known 


41 

























Table 16. DBP results at plant 1 (7/17/01) 


07/17/2001 

MRL a 

fjg/L 

Plant 1 n 

Compound 

Raw 

0 3 Eff 

Clear. Eff 

Fin. Water 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Halomethanes 










Chloromethane 

0.2 

ND d 

ND 

ND 

ND 

ND 


ND 


Bromomethane 

0.2 

ND 

ND 

ND 

ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 


ND 


Dibromomethane 

0.5 

NP 

ND 

ND 

ND 

ND 


ND 


Chloroform 6 

0.1 

ND 

0.1 

0.2 

0.4 

1 

1 

0.3 

0.4 

Bromodichloromethane 6 

0.1 

ND 

0.1 

0.7 

2 

3 

3 

2 

2 

Dibromochloromethane 6 

0.1 

NP 

ND 

1 

4 

4 

NR 9 

3 

NR 

Bromoform 6 

0.11 

NP 

ND 

0.8 

3 

3 

3 

3 

3 

THM4 f 


NP 

0.2 

3 

9 

11 

NR 

8 

NR 

Dichloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloroiodomethane 

0.25 

ND 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

Dibromoiodomethane 

0.5 

NP 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1-0.5 

ND 

ND 

0.2 

ND 

0.3 

ND 

ND 

ND 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 

ND 

ND 

ND 

ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halo acetic, acids 










Monochloroacetic acid 6 

2 



ND 

ND 

ND 


ND 


Monobromoacetic acid 6 

1 



ND 

ND 

ND 


ND 


Dichloroacetic acid 6 

1 



1.1 

2.2 

4.8 


2.2 


Bromochloroacetic acid 6 

1 



2.4 

2.2 

3.6 


3.8 


Dibromoacetic acid 6 

1 



4.2 

3.6 

4.3 


6.4 


Trichloroacetic acid® 

1 



ND 

ND 

1.2 


ND 


Bromodichloroacetic acid 

1 



ND 

ND 

1.1 


ND 


Dibromochloroacetic acid 

1 



ND 

ND 

ND 


ND 


Tribromoacetic acid 

2 



ND 

ND 

ND 


ND 


HAA5 h 




5.3 

5.8 

10 


9 


HAA9' 




7.7 

8.0 

15 


12 


DXA A 




7.7 

8.0 

13 


12 


TXAA k 




ND 

ND 

2.3 


ND 


Haloacetonitriles 










Chloroacetonitrile 

0.1 

NP 

NP 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

NP 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile 6 

0.10 

ND 

ND 

ND 

0.1 

0.2 

0.2 

0.1 

ND 

Bromochloroacetonitrile 6 

0.1 

ND 

ND 

ND 

0.3 

0.1 

0.3 

0.3 

0.2 

Dibromoacetonitrile 6 

0.14 

NP 

ND 

0.6 

0.6 

0.6 

0.6 

0.6 

0.4 

Trichloroacetonitrile 6 

0.1 

NP 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 

ND 


ND 




ND 

Dibromochloroacetonitrile 

0.5 

ND 

ND 


ND 




ND 

Tribromoacetonitrile 

0.5 

ND 

ND 


ND 




ND 

Haloacetaldehvdes 










Dichloroacetaldehvde 

0.22 

ND 

ND 

2 

0.2 

1 

2 

0.7 

2 

Bromochloroacetaldehvde 

0.1 

ND 

ND 

1 

0.4 

ND 

ND 

ND 

0.1 

Chloral hydrate 6 

0.1 

ND 

ND 

2 

ND 

ND 

ND 

ND 

ND 

T ribromoacetaldehvde 

0.1 

ND 

ND 

2 

0.1 

ND 

ND 

ND 

ND 


42 


































































Table 16 (continued) 


07/17/2001 

MRL a 

Plant 1° 

Compound 

mq/l 

Raw 

0 3 Eff 

Clear. Eff 

Fin. Water 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloketones 










ChloroDroDanone 

0.1 

ND 

ND 

0.1 

0.1 

0.1 

ND 

0.1 

ND 

1,1 -Dichloropropanone 6 

0.10 

ND 

ND 

0.2 

0.2 

0.3 

0.3 

0.2 

0.2 

1.3-DichloroDroDanone 

0.1 

ND 

ND 

0.5 

ND 

ND 

ND 

ND 

ND 

1 .l-DibromooroDanone 

0.10 

[SID 

ND 

0.3 

0.1 

ND 

ND 

ND 

ND 

1.1.1 -T richloroDroDanone 6 

0.1 

ND 

ND 

0.5 

0.1 

ND 

ND 

ND 

ND 

1.1.3-TrichloroDroDanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1.1-dichloroDroDanone 

0.1 

ND 

ND 

0.4 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T ribromopropanone 

0.29 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 .1.3-T ribromooroDanone 

0.14 

$ 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1,3.3-TetrachloroDroDanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1.1,3-TetrachloroDroDanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1,3.3-TetrabromoDroDanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 










Bromonitromethane 

0.1 

ND 

ND 

ND 

0.2 

ND 

0.1 

0.1 

0.1 

Dichloronitromethane 

0.1 

ND 

ND 

ND 

0.1 

0.2 

0.2 

ND 

0.2 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

0.2 

0.1 

0.1 

0.2 

0.1 

Dibromonitromethane 

0.10 

ND 

ND 

0.1 

0.5 

0.2 

0.2 

0.4 

0.2 

ChloroDicrin 6 

0.1 

0,1 

0.2 

0.1 

ND 

0.2 

0.1 

0.1 

0.2 

Bromodichloronitromethane 

0.5 

ND 

ND 


0.7 




0.9 

Dibromochloronitromethane 

0.5 

ND 

ND 


1.5 




1.7 

Bromojaicni^ 

0.5 

ND 

ND 


2.5 




2.8 

Miscellaneous ComDounds 










Methyl ethyl ketone 

0.5 

ND 

1 

ND 

ND 

ND 


ND 


Methyl tertiary butyl ether 

0.2 

ND 

ND 

ND 

ND 

ND 


ND 


1,1,2,2-Tetrabromo-2-chloroethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Benzvl chloride 

0.25 

ND 

NR 

ND 

ND 

ND 

NR 

ND 

NR 


r <0.5 = Detected by GC/MS below its MRL of 0.5 pg/L; interference problem with GC/ECD analysis 


43 














































Table 17. DBP results at plant 2 (7/17/01) 


07/17/2001 

MRL 

ijg/L 

Plant 2° 

Compound 

Filt. Eff 

Treat. Tank 

Fin. Water 

DS/Ave 

DS/Max 

SDS/Ave 

S DS/Max 

Halomethanes 









Chloromethane 

0.2 


ND 

ND 

ND 


ND 


Bromomethane 

0.2 


ND 

ND 

ND 


ND 


Bromochloromethane 

0.5 


ND 

ND 

ND 


ND 


Dibromomethane 

0.5 


ND 

ND 

ND 


ND 


Chloroform® 

0.1 

5 

6 

7 

7 

9 

8 

8 

Bromodichloromethane 8 

0.1 

9 

11 

13 

15 

16 

16 

16 

Dibromochloromethane® 

0.1 

NR 

7 

10 

11 

NR 

11 

NR 

Bromoform 8 

0.11 

2 

2 

2 

2 

2 

2 

2 

THM4 f 


NR 

26 

32 

35 

NR 

37 

NR 

Dichloroiodomethane 

0.5 

5 

4 

4 

3 

0.6 

3 

2 

Bromochloroiodomethane 

0.25 

NR 

1 

1 

1 

NR 

1 

NR 

Dibromoiodomethane 

0.5 

NR 

<0.5 r 

<0.5 

<0.5 

ND 

0.7 

NR 

Chlorodiiodomethane 

0.1-0.5 

0.4 

<0.5 

<0.5 

<0.5 

ND 

0.5 

NR 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 


ND 

ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 









Monochloroacetic acid 8 

2 


ND 

ND 

ND 


ND 


Monobromoacetic acid® 

1 


ND 

ND 

ND 


ND 


Dichloroacetic acid 8 

1 


12 

12 

12 


13 


Bromochloroacetic acid® 

1 


12 

11 

11 


12 


Dibromoacetic acid 8 

1 


6.2 

6.2 

6.2 


6.6 


Trichloroacetic acid® 

1 


9.2 

9.0 

7.5 


9.3 


Bromodichloroacetic acid 

1 


7.9 

7.8 

7.0 


8.3 


Dibromochloroacetic acid 

1 


3.7 

3.6 

3.0 


3.8 


Tribromoacetic acid 

2 


ND 

ND 

ND 


ND 


HAA5 h 



27 

27 

26 


29 


HAA9' 



51 

50 

47 


53 


DXAA j 



30 

29 

29 


32 


TXAA k 



21 

20 

18 


21 


Haloacetonitriles 









Chloroacetonitrile 

0.1 

ND 

0.1 

0.1 

0.1 

0.1 

0.1 

0.1 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile® 

0.10 

1 

2 

2 

2 

2 

2 

2 

Bromochloroacetonitrile 8 

0.1 

1 

2 

2 

2 

2 

2 

2 

Dibromoacetonitrile® 

0.14 

1 

2 

2 

2 

2 

1 

2 

T richloroacetonitrile 8 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 



ND 

ND 



ND 

Dibromochloroacetonitrile 

0.5 



ND 

ND 



ND 

T ribromoacetonitrile 

0.5 



ND 

ND 



ND 

Haloacetaldehvdes 









Dichloroacetaldehyde 

0.22 

2 

1 

1 

0.9 

1 

1 

2 

Bromochloroacetaldehyde 

0.1 

2 

1 

1 

1 

0.6 

1 

1 

Chloral hydrate 8 

0.1 

1 

2 

2 

2 

1 

2 

z 

T ribromoacetaldehyde 

0.1 

0.3 

0.2 

0.2 

0.1 

ND 

0.1 

0.1 


44 
































































Table 17 (continued) 


07/17/2001 

MRL 

mq/l 


3 lant 2° 

Compound 

Filt. Eff 

Treat. Tank 

Fin. Water 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Halnketnnes 









Chloropropanone 

0.1 

ND 

ND 

0.1 

0.1 

0.1 

0.1 

0.1 

1.1 -Dichloropropanone 6 

0.10 

0.7 

0.8 

0.7 

0.5 

0.5 

0.6 

0.7 

1.3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

0.10 

0.6 

0.3 

0.3 

0.2 

ND 

0.2 

0.1 

1,1,1-Trichloropropanone® 

0.1 

0.7 

1 

1 

0.9 

0.2 

0.8 

0.7 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

l-Bromo-1,1-dichloropropanone 

0.1 

NR 

1 

1 

0.3 

ND 

ND 

ND 

1,1,1-Tribromopropanone 

0.29 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1.3-T ribromoorooanone 

0.14 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-Tetrachloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrabromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 









Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

0.2 

0.2 

0.2 

0.2 

0.1 

0.2 

0.1 

Bromochloronitromethane 

0.1 

0.1 

0.1 

0.1 

0.1 

0.1 

0.1 

0.1 

Dibromonitromethane 

0.10 

0.1 

0.1 

0.1 

0.1 

ND 

ND 

ND 

Chloropicrin 6 

0.1 

0.1 

0.2 

0.2 

0.2 

0.1 

0.1 

0.2 

Bromodichloronitromethane 

0.5 



0.8 

0.6 



0.8 

Dibromochloronitromethane 

0.5 



1.0 

0.8 



0.9 

Bromopicrin 

0.5 



ND 

ND 



ND 

Miscellaneous Compounds 









Methyl ethyl ketone 

0.5 


ND 

ND 

ND 


ND 


Methyl tertiary butyl ether 

0.2 


ND 

ND 

ND 


ND 


1,1,2,2-Tetrabromo-2-chloroethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Benzyl chloride 

0.25 

NR 

ND 

ND 

ND 

NR 

ND 

NR 


45 










































Table 18. Additional target DBP results (pg/L) at the EPA Region 9 treatment plants 
(7/17/01) 


7/17/01 

Plant l a 

Plant 2 a 

Compound 

Raw 

OE 

FE 

PE 

DS 

SDS 

FI 

TT 

PE 

DS 

SDS 

Monochloroacetaldehyde 












Dichloroacetaldehyde 












Bromochloroacetaldehyde 












3,3-Dichloropropenoic acid 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

Bromo chloromethylacetate 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

2,2-Dichloroacetamide 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

TOX (pg/L as Cf) 

NA 

NA 

10.2 

21.1 

25.3 

43.2 

75.6 

84.5 

91.3 

106 

114 

Cyanoformaldehyde 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

5-Keto-l-hexanal 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

6-Hydroxy -2-hexanone 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

Dimethylglyoxal 

<0.4 

0.8 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

trans- 2-Hexenal 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 


a SDS testing of finished water at maximum detention time 


Table 19. Halogenated furanone results (pg/L) at the EPA Region 9 treatment plants 
(7/17/01) 


7/17/01 

Plant 1 

Plant 2 

Compound 

FE 

PE 

FE 

DS 

Mucochloric acid (ring) 

<0.04 

<0.04 

<0.04 

<0.04 

Mucochloric acid (open) 

<0.04 

<0.04 

0.07 

<0.04 

MX 

<0.04 

<0.04 

0.12 

0.07 

ZMX 

<0.04 

<0.04 

0.05 

<0.04 

EMX 

<0.04 

<0.04 

<0.04 

<0.04 


46 







































Table 20. DBP results at plant 1 (3/19/02) 


03/19/2002 

MRL a 

Plant 1 n 

Compound 

MQ/L 

Raw 

0 3 Eff 

Clear. Eff 

Fin. Water 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Halomethanes 










Chloromethane 

0.2 

z 

o 

Q. 

ND 

ND 

ND 

ND 


ND 


Bromomethane 

0.2 

ND 

ND 

ND 

ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 


ND 


Dibromomethane 

0.5 

ND 

ND 

ND 

ND 

ND 


ND 


Chloroform 6 

0.2 

ND 

1 

2 

2 

3 

NR 9 

2 

2 

Bromodichloromethane 6 

0.2 

ND 

1 

2 

3 

4 

NR 

4 

5 

Dibromochloromethane® 

0.2 

ND 

0.4 

2 

3 

4 

NR 

4 

7 

Bromoform 6 

0.2 

ND 

ND 

0.6 

0.8 

2 

NR 

2 

1 

THM4 f 


ND 

2 

7 

9 

13 

NR 

12 

15 

Dichloroiodomethane 

0.25 

NP 

0.3 

ND 

NR 

ND 

NR 

ND 

0.4 

Bromochloroiodomethane 

0.25 

NP 

ND 

ND 

ND 

<0.25® 

0.6 

<0.25 

ND 

Dibromoiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.5 

NP 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 

ND 

ND 

ND 

ND 

ND 


ND 

ND 

T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 










Monochloroacetic acid 6 

2 



ND 

ND 

ND 


ND 


Monobromoacetic acid 6 

1 



ND 

ND 

ND 


ND 


Dichloroacetic acid® 

1 



1.9 

2.1 

4.2 


3.9 


Bromochloroacetic acid® 

1 



2.3 

1.3 

3.9 


3.6 


Dibromoacetic acid® 

1 



2.7 

2.1 

5.4 


5.9 


Trichloroacetic acid® 

1 



1.5 

1.6 

1.6 


2.0 


Bromodichloroacetic acid 

1 



2.0 

1.0 

1.6 


2.3 


Dibromochloroacetic acid 

1 



ND 

ND 

1.8 


2.0 


Tribromoacetic acid 

2 



ND 

ND 

ND 


ND 


HAA5 h 




6.1 

5.8 

11 


12 


HAA9 1 




10 

8.1 

19 


20 


DXAA j 




6.9 

5.5 

14 


13 


TXAA k 




3.5 

2.6 

5.0 


6.3 


Haloacetonitriles 










Chloroacetonitrile 

0.1 

NP 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile® 

0.2 

ND 

0.2 

ND 

0.2 

ND 

NR 

ND 

0.5 

Bromochloroacetonitrile® 

0.5 

ND 

ND 

<0.5 

0.8 

1 

2 

1 

2 

Dibromoacetonitrile 6 

0.1 

ND 

ND 

0.5 

0.6 

0.8 

0.8 

0.3 

0.8 

T richloroacetonitrile 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 

ND 


ND 





Dibromochloroacetonitrile 

0.5 

NP 

ND 


ND 





T ribromoacetonitrile 

0.96 

ND 

ND 


ND 





Haloacet^l^hy^g 










Dichloroacetaldehvde 

0.98 

ND 

ND 

1 

1 

2 

2 

2 

2 

Bromochloroacetaldehvde 

0.5 

ND 

0.1 

0.9 

1 

2 

2 

2 

2 

Chloral hvdrate® 

0.1 

ND 

0.2 

0.7 

0.6 

0.5 

0.8 

1 

1 

T ribromoacetaldehvde 

0.1 

ND 

ND 

0.8 

0.5 

ND 

ND 

ND 

ND 


47 
































































Table 20 (continued) 


03/19/2002 

MRL a 

Plant 1 n 

Compound 

mq/l 

Raw 

0 3 Eff 

Clear. Eff 

Fin. Water 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Haloketones 










ChloroDroDanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-DichloroDrooanone e 

0.10 

ND 

0.4 

NR 

0.8 

NR 

NR 

1 

2 

1,3-DichloroDroDanone 

0.1 

ND 

ND 

0.2 

ND 

ND 

ND 

ND 

ND 

1.1-DibromoDrooanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1.1 -T richloroDroDanone 6 

0.1 

ND 

0.5 

<0.5 

0.5 

0.6 

0.6 

0.3 

0.3 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1.1-dichloroDroDanone 

0.1 

ND 

ND 

0.1 

0.2 

ND 

ND 

ND 

ND 

1.1.1-TribromoDroDanone 

NA'i 

ND 

ND 

NR 

ND 

NR 

NR 

NR 

ND 

1.1.3-TribromoDrooanone 

0.1 

ND 

ND 

0.5 

ND 

ND 

ND 

ND 

ND 

1.1,3.3-TetrachloroDroDanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1.1,3-TetrachloroDroDanone 

0.10 

ND 

ND 

0.4 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrabromopropanone 

0.1 

ND 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 










Chloronitromethane 

NA 

ND 

ND 

ND 

ND 

ND 


ND 

ND 

Bromonitromethane 

0 1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 


ND 

ND 

ND 

0.2 

0.2 

0.3 

0.1 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

0.1 

0.2 

ND 

ND 

ND 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

0.1 

ND 

ND 

ND 

ND 

Chloropicrin® 

Vf 

ND 

NR 

ND 

ND 

<0.5 

NR 

<0.5 

NR 

Bromodichloronitromethane 

0.5 

ND 

ND 


ND 





Dibromochloronitromethane 


ND 

ND 


ND 





Bromopicrin 

0.5 

ND 

ND 


ND 


% 



Miscellaneous Comnounds 










Methvl ethvl ketone 

0.5 

ND 

ND 

ND 

ND 

ND 


ND 


Methvl tertiary butvl ether 

0.2 

ND 

ND 

ND 

ND 

ND 


ND 


1,1,2,2-Tetrabromo-2-chloroethane 

0.54 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Benzyl chloride 

0.5 

ND 

ND 

ND 

ND 

ND 

NR 

ND 

ND 


s <0.25 or <0.5 or <1 = Detected by GC/MS below its MRL of 0.25 or 0.5 or 1 uq/L; 
quality assurance problem with gas chromatograph method 
! NA = Not available. 


48 














































Table 21. DBP results at plant 2 (3/19/02) 


03/19/2002 

MRL 

pg/L 

Plant 2° 

Compound 

Filt. Eff 

Treat. Tank 

Fin. Water 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Halomethanes 









Chloromethane 

0.2 


ND 

ND 

ND 


ND 


Bromomethane 

0.2 


ND 

ND 

ND 


ND 


Bromochloromethane 

0.5 


ND 

ND 

ND 


ND 


Dibromomethane 

0.5 


ND 

ND 

ND 


ND 


Chloroform 6 

0.2 

NR 

15 

16 

28 

NR 

25 

34 

Bromodichloromethane® 

0.2 

NR 

17 

19 

23 

NR 

25 

27 

Dibromochloromethane 6 

0.2 

NR 

6 

7 

8 

NR 

8 

11 

Bromoform 8 

0.2 

NR 

0.7 

0.6 

0.7 

NR 

0.9 

0.4 

THM4 f 

0 

NR 

39 

43 

60 

NR 

59 

72 

Dichloroiodomethane 

0.25 

NR 

2 

2 

2 

2 

3 

2 

Bromochloroiodomethane 

0.25 

1 

1 

1 

1 

2 

1 

2 

Dibromoiodomethane 

0.5 

0.7 

0.5 

0.6 

<0.5 

ND 

0.5 

ND 

Chlorodiiodomethane 

0.1 

NR 

<0.5 

<0.5 

<0.5 

NR 

<0.5 

NR 

Bromodiiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 


ND 

ND 

ND 


ND 

ND 

T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 









Monochloroacetic acid 8 

2 


ND 

2.1 

ND 


2.2 


Monobromoacetic acid 6 

1 


ND 

ND 

ND 


ND 


Dichloroacetic acid 8 

1 


18 

19 

20 


22 


Bromochloroacetic acid 6 

1 


9.6 

6.1 

6.2 


10 


Dibromoacetic acid 8 

1 


3.5 

3.4 

3.7 


4.0 


Trichloroacetic acid 6 

1 


14 

13 

13 


16 


Bromodichloroacetic acid 

1 


9.7 

9.2 

9.5 


11 


Dibromochloroacetic acid 

1 


2.7 

2.4 

2.4 


3.0 


Tribromoacetic acid 

2 


ND 

ND 

ND 


ND 


HAA5 h 

0 


36 

38 

37 


44 


HAA9' 

0 


58 

55 

55 


68 


DXAA 1 

0 


31 

29 

30 


36 


TXAA k 

0 


26 

25 

25 


30 


Haloacetonitriles 









Chloroacetonitrile 

0.1 

ND 

0.1 

0.1 

0.1 

0.2 

0.2 

0.2 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile 6 

0.2 

NR 

1 

2 

2 

NR 

2 

3 

Bromochloroacetonitrile 6 

0.5 

2 

1 

2 

2 

1 

1 

2 

Dibromoacetonitrile 6 

0.1 

0.8 

0.5 

0.9 

0.5 

0.7 

0.6 

1 

Trichloroacetonitrile 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 



ND 

ND 



ND 

Dibromochloroacetonitrile 

0.5 



ND 

ND 



ND 

T ribromoacetonitrile 

0.96 



ND 

ND 



ND 

Haloacetaldehydes 









Dichloroacetaldehvde 

0.98 

2 

2 

2 

2 

2 

2 

3 

Bromochloroacetaldehvde 

0.5 

0.6 

0.7 

0.5 

ND 

ND 

ND 

ND 

Chloral hydrate 8 

0.1 

2 

4 

3 

4 

4 

4 

4 

T ribromoacetaldehyde 

0.1 

ND 

0.4 

0.1 

ND 

ND 

ND 

ND 


49 

































































Table 21 (continued) 


03/19/2002 

MRL 

Mg/L 


=lant 2° 

Compound 

Filt. Eff 

Treat. Tank 

Fin. Water 

DS/Ave 

DS/Max 

S DS/Ave 

S DS/Max 

Halnkptnnes 









Chloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1 -Dichlorocronanone 6 

0.10 

NR 

2 

1 

1 

NR 

1 

1 

1.3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1.1-Trichloropropanone e 

0.1 

NR 

3 

3 

2 

NR 

2 

2 

1.1.3-Trichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

0.1 

0.4 

<1 

0.9 

ND 

ND 

ND 

ND 

1.1.1 -T ribromopropanone 

NA 

NR 

NR 

ND 

ND 

NR 

NR 

ND 

1.1.3-Tribromopropanone 

0.1 

0.2 

ND 

0.1 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrachloropropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-T etrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrabromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 









Chloronitromethane 

NA 


ND 

ND 

ND 


ND 

ND 

Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

0.2 

0.3 

0.2 

0.2 

0.3 

0.3 

0.2 

Bromochloronitromethane 

0.1 

0.2 

ND 

0.3 

ND 

0.1 

ND 

ND 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin® 

0.5 

NR 

<0.5 

<0.5 

<0.5 

NR 

0.5 

NR 

Bromodichloronitromethane 

0.5 



1 

0.8 



1 

Dibromochloronitromethane 

2 



ND 

ND 



ND 

Bromopicrin 

0.5 



ND 

ND 



ND 

Miscellaneous Compounds 









Methyl ethyl ketone 

0.5 


ND 

ND 

ND 


ND 


Methyl tertiary butyl ether 

0.2 


ND 

ND 

ND 


ND 


1.1.2.2-Tetrabromo-2-chloroethane 

0.54 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Benzyl chloride 

0.5 

NR 

ND 

ND 

ND 

NR 

ND 

NR 


50 











































Table 22. Additional Target DBP Results (pg/L) at the EPA Region 9 treatment plants 
(3/19/02) 


3/19/02 

Plant l a 

Plant 2 b 

Compound 

Raw 

OE 

FE 

PE 

DS 

FE 

TT 

PE 

DS/a 

DS/m 

SDS 

Monochloroacetaldehyde 

0 

1.8 

2.2 

2.4 

0 

0.2 


0 


0.3 


Dichloroacetaldehyde 

0 

0 

0 

3.5 

1.5 

2.9 


4.2 


5.8 


Bromochloroacetaldehyde 

0 

0 

0 

1.8 

3.0 

1.3 


1.1 


1.2 


3,3-Dichloropropenoic acid 

0 


0 

0 

0 

0 


0 


0 


Bromochloromethylacetate 

0 


0 

0 

0 

0 


0 


0 


Monochloroacetamide 

0 


0 

0 

0 

0 


0 


0 


Monobromoacetamide 

0 


0 

0 

0 

0 


0 


0 


2,2-Dichloroacetamide 

0 


0 

0.6 

1.1 

1.2 


3.9 


4.5 


Dibromoacetamide 

0 


0.1 

1.6 

1.6 

0.4 


0.8 


0.7 


Trichloroacetamide 

0 


0.1 

0.1 

0.2 

0.3 


0.3 


0.3 


TOX (pg/L as Cl') 

11.3 


18.3 

145 

164 

191 

234 

200 

164 

243 

246 

TOBr (pg/L as Br) 

4.6 


2.0 

79.7 

50.0 

67.0 

72.0 

76 

76 

84 

86 

TOC1 (pg/L as Cl') 

9.3 


20.5 

87.2 

142 

116 

202 

185 

155 

195 

204 

Cyanoformaldehyde 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

5-Keto-l-hexanal 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

6-Hydroxy -2-hexanone 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

Dimethylglyoxal 

<0.1 

0.4 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

/ra«s-2-Hexenal 

<0.1 

<0.1 

<0.1 

<0.1 

1.0 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 


a Plant 1 DS sampled at maximum detention time 

b Plant 2 DS sampled at average (a) and maximum (m) detention times 


Table 23. Halogenated furanone results (pg/L) at the EPA Region 9 treatment plants 
(3/19/02) _ 


3/19/02 

Plant 1 

Plant 2 

Compound 

FE 

PE 

FE 

PE 

DS/max 

BMX-1 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

BEMX-1 

<0.02 

0.02 

<0.02 (0.01) 

0.29 

0.18 

BMX-2 

<0.02 

<0.02 

<0.02 (0.01) 

0.02 

<0.02 (0.01) 

BEMX-2 

<0.02 

<0.02 

<0.02 (0.01) 

0.03 

0.04 

BMX-3 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

BEMX-3 

<0.02 

<0.02 (0.01) 

0.04 

0.17 

0.06 

MX 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

EMX 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

ZMX 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

Ox-MX 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

Mucochloric acid (ring) 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

Mucochloric acid (open) 

<0.02 

0.03 

0.09 

0.10 

0.11 


51 




















































Table 12 (10/30/00), Table 18 (7/17/01), and Table 22 (3/19/02) show results for additional 
target DBPs that were analyzed at the University of North Carolina (UNC). Table 15 (1/23/01) 
shows results from broadscreen DBP analyses conducted at the U.S. Environmental Protection 
Agency (USEPA). Table 19 (7/17/01) and Table 23 (3/19/02) show results for halogenated 
furanones that were analyzed at UNC. 


Summary of tables for halogenated or 

panic and other nonhalogenated organic DBPs 

DBP Analyses (Laboratory) 

10/30/00 

1/23/01 

7/17/01 

3/19/02 

Halogenated organic DBPs (MWDSC) 

Tables 10-11 

Tables 13-14 

Tables 16-17 

Tables 20-21 

Additional target DBPs (UNC) 

Table 12 


Table 18 

Table 22 

Halogenated furanones (UNC) 



Table 19 

Table 23 

Broadscreen analysis (USEPA) 


Table 15 




Halomethanes. Figure 7 shows the effect of the different treatment/disinfection scenarios 
at plant 1 and at plant 2 (for July 2001) on trihalomethane (THM) formation and speciation. The 
use of ozonation/chloramination significantly reduced THM formation. However, at plant 1, 
there was a shift to the formation of the more brominated species. Jacangelo and colleagues 
(1989) also observed that pre-ozonation in bromide-containing waters could result in a shift in 
speciation upon post-chlorination. In addition, because chlorine was not added until after 
coagulation at plant 1, the bromide-to-TOC ratio was higher (since coagulation removes TOC, 
but not bromide), which can also result in a shift in THM speciation (Symons et al., 1993). 

Figure 7 

Effect of Ozone/Chlorine/Chloramines at Plant 1 and 
Chlorine/Chloramines at Plant 2 on Trihalomethane Formation 
and Speciation in Finished Waters (July 17, 2001) 



52 



















































Figure 8 shows the effect of bromide on THM formation and speciation in the finished 
water at plant 2 for the January 2001, July 2001, and March 2002 samplings. The increase in 
bromide resulted in more THM formation, as well as a shift in speciation. For example, 
dibromochloromethane and bromoform formation were significantly higher when the bromide 
level in the source water increased. 


Figure 8 

Impact of Bromide on Trihalomethane Speciation 
in Plant 2 Effluent: January 2001 - March 2002 



In addition, low or sub-pg/L levels of iodinated THMs were detected, primarily at plant 
2. (At plant 1 and plant 2, saltwater intrusion is the source of bromide and, thus, should also be a 
source of iodide). For example, in January 2001 (bromide = 0.40 mg/L), 1 pg/L of iodoform was 
detected in the ozone contactor effluent at plant 1, but was not detected (with a minimum 
reporting level [MRL] of 0.7 pg/L) in downstream locations. However, 0.3 and 0.2 pg/L of 
dichloroiodo- and bromochloroiodomethane, respectively, were detected in the chloraminated, 
distributed water. Broadscreen GC/MS analyses also revealed the presence of 
dichloroiodomethane and bromochloroiodomethane, as well as dibromoiodomethane in finished 
water from plant 1 (January 2001) (Table 15). At plant 2, 0.5 and 0.6 pg/L of dichloroiodo- and 
bromochloroiodomethane, respectively, were detected in the plant after chlorination, and 0.6 
pg/L of dibromoiodomethane was detected after chloramination. 

Iodide is oxidized to hypoiodous acid in the presence of ozone, chlorine, or chloramines. 
Bichsel and von Gunten (2000) found that when ozone (0 3 ,1.0 mg/L) was used on a low-TOC 
(1.3 mg/L) water ( 03 iTOC = 0.77 mg/mg), no iodinated THMs were detected and >90 % of the 
iodide was transformed to iodate, whereas chlorine led to the formation of iodate and iodinated 
THMs. At plant 1 in January 2001, 2.5 mg/L ozone was used on a moderate-TOC (4.5 mg/L) 


53 














water ( 03 :T 0 C = 0.56 mg/mg). Although iodate was not measured in this study, the formation 
of iodoform after ozonation and other iodinated THMs after chloramination suggests that the 
lower C> 3 :TOC ratio did not result in a quantitative conversion of iodide to iodate. However, the 
use of ozone at plant 1 did result in the formation of less iodinated THMs in the finished water 
than at plant 2. 

Figure 9 shows the THM speciation—including the iodomethanes—at plant 2 in July 
2001 (bromide = 0.14 mg/L). Bromodichloromethane was the major species of the four 
regulated THMs, and dichloroiodomethane was the major iodomethane. In both cases, the major 
THM formed for each group of halomethanes was dichlorinated, with either a bromine or iodine 
atom as the third halogen. 


Figure 9 


Dibromoiodomethane 

2 % 

Bromochloroiodomethane _ 
2 % 

Chlorodiiodomethane 
1 % 

Dichloroiodomethane 
7% 

Bromoform 
5% 


Bromodiiodomethane 

0 % 


Chloroform 

19% 


Dibromochloromethane 
26% 



Bromodichloromethane 
38% 


Trihalomethane Speciation at Plant 2 
SDS (Average Detention Time) Sample (July 17, 2001) 


Haloacids. Figure 10 shows the effect of bromide (Br) on haloacetic acid (HAA) 
formation and speciation in the finished water at plant 2 for the October 2000 and the January 
2001 samplings. For example, tribromoacetic acid was detected when the bromide level in the 
source water increased, whereas it was not detected when the bromide level was lower. In 
addition, there was a shift to the formation of the other bromine-containing HAAs. 

At plant 2, the sum of the dihalogenated HAAs (DXAAs) was somewhat higher than the 
sum of the trihalogenated HAAs (TXAAs), whereas at plant 1 the formation of HAAs was 
almost due only to the DXAAs. In other research, ozonation had been shown to be able to 
destroy THM and TXAA precursors better than DXAA precursors (Reckhow and Singer, 1984). 


54 






Figure 10 


Effect of Bromide on HAA Formation and Speciation in Finished Water 
at Plant 2: 10/30/00 Br' = 0.16 mg/L; 1/23/01 Br' = 0.40 mg/L 





r> 




<? 

vO' 


,rP 


^ 0 X °' 


xO N 




* yyyy 


O w rP'’ /&■ WN.O 




<9 




s * </>V 




& 


1 / 23/2001 

10 / 30/2000 


Similarly, chloramination has been shown to be more effective at controlling the formation of 
THMs and TXAAs than the formation of DXAAs (Krasner et al., 1996). 

In addition to the target HAAs, other haloacids were detected in selected drinking water 
samples by the broadscreen GC/MS methods (Table 15). Plant 1—whose source water had 0.40 
mg/L bromide in January 2001—had numerous brominated acids. Fourteen brominated acids 
(2,2-dibromopropanoic acid, 3,3-dibromopropenoic acid, c/s-2,3-dibromopropenoic acid, 
tribromopropenoic acid, 2-bromobutanoic acid, /ra/7s-4-bromo-2-butenoic acid, c/5-4-bromo-2- 
butenoic acid, 2,3-dibromo-2-butenoic acid, bromodichlorobutenoic acid, bromochloro-4- 
oxopentanoic acid, 3,3-dibromo-4-oxopentanoic acid, 2-bromobutenedioic acid, trans- 2,3- 
dibromobutenedioic acid, c/s-2-bromo-3-methylbutenedioic acid) had not been previously 
reported in drinking water. Several of these bromo-acids were also seen in finished waters from 
plant 11 (EPA Region 6), and also in drinking waters from Israel that had been treated with 
chlorine or chlorine dioxide-chloramine (Richardson et al., submitted). 

October 2000 results from UNC indicated the presence of another target halo-acid, 3,3- 
dichloropropenoic acid, at levels of 0.1 and 0.7 pg/L, respectively, in finished waters from the 
plant 1 and plant 2 (Table 12). 

Haloacetonitriles. In other DBP research, haloacetonitriles (HANs) were found to be 
produced at approximately one-tenth the level of the THMs (Krasner et al., 1989). This was also 
observed in the plant 1 and plant 2 samples. Dichloro-, bromochloro-, and dibromoacetonitrile— 


55 
















Information Collection Rule (ICR) DBPs—were detected at both treatment plants. 
Trichloroacetonitrile—another ICR DBP—was not detected; likewise, the brominated analogues 
of trichloroacetonitrile were not detected. Sub-pg/L levels of chloroacetonitrile were detected at 
plant 2 in July 2001 and March 2002. 

Haloketones. In addition to the formation of low levels of haloketone (HK) compounds 
from the ICR, low levels of 1,1,3,3-tetrabromopropanone were detected in January 2001, 
primarily at plant 2. The concentration of this HK at plant 2 decreased in the distribution system, 
and was not detected in the SDS samples. The distribution-system and SDS samples were at a 
pH of 8.5 to 9.0, thus the disappearance of this HK was probably due to base-catalyzed 
hydrolysis. (For example, Croue and Reckhow (1989) found that 1,1,1-trichloropropanone— 
another HK—undergoes base-catalyzed hydrolysis at pH 8.5.) During the October 2000 
sampling, this brominated HK was not detected, instead its chlorinated analogue, 1,1,3,3- 
tetrachloropropanone, was detected. Thus, the higher bromide level in the source water in 
January 2001 also changed the speciation of this HK. 

Low levels of other HKs were also detected in July 2001 (Figure 11). These included a 
monohalogenated HK (i.e., chloropropanone) and other di- and trihalogenated HKs in which the 
halogens were not all on the same carbon atom and/or there was bromine substitution. 


Figure 11 


Haloketone Speciation at Plant 1 
Clearwell Effluent Sample (July 17, 2001) 

Tetrahalogenated species not detected 


1-Bromo-1,1- 

dichloropropanone 

20 % 


1,1,1 -T ribromopropanone 
0 % 

1,1,3-T ribromopropanone 
0 % 

Chloropropanone 
5% 


1,1,3-Tri chloropropanone 
0 % 


1,1,1-Trichloropropanone 
25% 



1,1 -Dichloropropanone 
10 % 


1,3-Dichloropropanone 
25% 


1,1 -Dibromopropanone 
15 % 


In addition to the target HKs, other HKs were detected by the broadscreen GC/MS 
methods (Table 15). A number of these HKs were analogous to the di-, tri-, and tetrahalogenated 


56 



HKs quantified by MWDSC, except that these were brominated or mixed bromochloro species. 
For example, in January 2001, when the raw-water bromide was at 0.40 mg/L, MWDSC detected 
1,1-dichloro-, 1,1,1-trichloro-, and 1,1,3,3-tetrabromopropanone after chloramination and 
ozonation at plant 1. Broadscreen GC/MS analysis of this same water also detected two 
brominated analogues of 1,1-dichloropropanone, two brominated analogues of 1,1,1- 
trichloropropanone, and a bromochloro analogue of 1,1,3,3-tetrabromopropanone. Most were 
observed in the finished water that had been treated with secondary chlorine and chloramine, but 
some were also seen in waters from the ozone contactor effluent. The chlorinated species were 
likely formed by the twice-a-week treatment of the flocculation and sedimentation basins with 
chlorine (which was applied at the ozone contactor effluent) to control algal growth, and not by 
the treatment with ozone. Alternatively, the brominated species may have been formed by 
ozone, as ozone can oxidize bromide to hypobromous acid, which can react with TOC to form 
brominated DBPs. 

Haloaldehydes. Figure 12 shows the impact of bromide on haloacetaldehyde speciation 
in the plant effluent of plant 2. When the bromide level was the highest (0.40 mg/L), there was a 
significant formation of bromochloro- and tribromoacetaldehyde. When the bromide 

Figure 12 

Impact of Bromide on Haloacetaldehyde Speciation 
in Plant 2 Effluent: January 2001 - March 2002 



concentration was lower (0.12-0.14 mg/L), both of these brominated species were formed at 
lower levels and the formation of the chlorinated species (dichloroacetaldehyde and chloral 
hydrate) were the major haloacetaldehydes produced. 


57 


















Likewise, when the bromide level was the highest, there was a significant formation of 
the bromine-containing THMs (bromodichloromethane, dibromochloromethane, and 
bromoform) (Figure 8). When the bromide concentration was lower, bromoform was formed at 
lower levels, and the formation of the chlorine-containing species (chloroform and 
bromodichloromethane) were typically the major THMs produced. 

In January 2001, tribromoacetaldehyde decreased in concentration in both sets of 
distribution-system and SDS samples, whereas the dihalogenated acetaldehydes increased in 
concentration in the distribution-system and SDS samples for plant 1. Moreover, the 
concentration of bromochloroacetaldehyde was higher in the distribution-system and SDS 
samples at plant 1 than at MSWTP. The results for tribromoacetaldehyde are consistent with the 
research of Xie and Reckhow (1996), who found that tribromoacetaldehyde degraded quickly at 
pH 9.0. In other research, acetaldehyde (an ozone by-product) was found to react with chlorine 
to form chloroacetaldehyde, which in the presence of free chlorine rapidly reacted to form 
chloral hydrate (McKnight and Reckhow, 1992). At plant 1, chlorine (in the presence of 
ammonia and bromide) may have reacted with acetaldehyde formed by the ozonation process to 
produce dichloro- and bromochloroacetaldehyde. 

In addition to the target haloacetaldehydes, another brominated aldehyde (2-bromo- 
2-methylpropanal) was detected by the broadscreen GC/MS methods (Table 15). 

Halonitromethanes. In addition to low levels of chloropicrin (trichloronitromethane) (an 
ICR DBP), low or sub-pg/L levels of other halonitromethanes (HNMs) were detected in the 
selected samples (Figure 13). Although ozone/chlorine/chloramines at plant 1 produced less 
THMs than chlorine/chloramines produced at plant 2 (Figure 7), a higher concentration of the 
trihalogenated HNMs was detected at plant 1 in July 2001 (Figure 13) (this was not the situation 
in March 2002). In other research, pre-ozonation was found to increase chloropicrin formation 
upon post-chlorination (Hoigne and Bader, 1988). In addition, the speciation of the 
trihalogenated HNMs was similar to the speciation of the THMs. At plant 2, the bromochloro 
species predominated, whereas at plant 1 there was more of a shift to the formation of the more 
fully brominated species. 


58 


Figure 13 


Effect of Ozone/Chlorine/Chloramines at Plant 1 and 
Chlorine/Chloramines at Plant 2 on Halonitromethane Formation and 
Speciation in Finished Waters (July 17, 2001) 



Halogenatedfuranones. Tables 19 and 23 show results for halogenated furanones in the 
July 2001 and March 2002 samplings for the EPA Region 9 treatment plants. Data are included 
for 3-chloro-4-(dichloromethyl)-5-hydroxy-2[5H]-furanone, otherwise known as MX; (E)-2- 
chloro-3-(dichloromethyl)-4-oxobutenoic acid, otherwise known as EMX; (Z)-2-chloro-3- 
(dichloromethyl)-4-oxobutenoic acid (ZMX); the oxidized form of MX (Ox-MX); brominated 
forms of MX and EMX (BMXs and BEMXs); and mucochloric acid (MCA), which can be found 
as a closed ring or in an open form. Results are displayed graphically in Figure 14. 

In July 2001, 3-chloro-4-(dichloromethyl)-5-hydroxy-2[5H]-furanone, otherwise known 
as MX, was detected at plant 2 but not at plant 1 (with an MRL of 0.04 pg/L) (Table 19; 

Figure 14). This is probably because ozone in the plant 1 treatment scheme removes MX 
precursors from the raw TOC, while chlorine in the plant 2 treatment scheme reacts with the raw 
TOC to form MX . Likewise, plant 1 produced less THMs than plant 2 (Figure 7). The filter 
effluent sample from plant 2 contained a higher concentration of MX (120 ng/L) than reported in 
a survey of Australian waters (<90 ng/L) (Simpson and Hayes, 1998). However, water quality 
and treatment/disinfection schemes may be different in Australia than in the United States. In 
particular, regulatory requirements in Australia are significantly different than in the United 
States. MX appears to degrade between the filter effluent and the distribution system (DS)/ 
average sample of plant 2. However, water in the distribution system may represent a blend of 
water from more than one treatment plant. In addition, water in the distribution system may 
represent water produced at plant 2 on a previous day, as the survey was not set up to follow a 
“plug” of water per se. The second sampling of plant 1 and plant 2 (March 2002) for 


59 















halogenated furanones showed similar trends, such as removal of MX-analogue precursors by 
ozonation in plant 1, when compared to plant 2 (Table 23, Figure 15). Overall, plant 2 exhibited 
higher concentrations of mucochloric acid (MCA open) and brominated MX-analogues than 
plant 1. Within the distribution system of plant 2, BEMX-1 appeared to decrease (from 290 ng/L 
in the plant effluent to 180 ng/L in the DS/maximum sample) and BEMX-3 appeared to decrease 
(from 170 ng/L in the plant effluent to 60 ng/L in the DS/maximum sample). Because TOC and 
bromide levels in the source water of this treatment plant can vary frequently (Krasner et al., 
1994)—as well as the pH of the water (which can significantly vary on a diurnal basis)— 
differences between the plant effluent and the distribution system (particularly at a maximum 
detention time) may be due (in part) to a comparison of different “packets” of water treated at 
different points in time. Alternatively, analysis of SDS samples for halogenated furanones 
would have allowed for a more direct assessment of the impact of distribution system detention 
time, etc., on the formation and stability of these DBPs. 

Figure 14 


Plant 1 and Plant 2 (7/17/01) 


■ MX 1 ZMX El EMX DMCA ring □ MCA open 


c 

o 

re 


c 

o 

o 

c 

o 

o 


4 > 

id 

c o> 
re i 


LL 

■o 

0 ) 

re 

c 

(V 

O) 

o 

re 

X 


0.30 

0.25 

0.20 

0.15 

0.10 

0.05 

0.00 



FE 

PE 

FE 

DS/ave 

03+Filter 

NaOCI+NH3 

NaOCI+Filter 

NaOCI+NH3 

Plant 1 

Plant 1 

Plant 2 

Plant 2 


Sampling Point 


60 




























Halogenated Fu 


Figure 15 

Plant 1 and Plant 2 (3/19/02) 


■ BMX-1 

HBEMX-1 

■ BMX-2 

M BEMX-2 

□ BMX-3 □ BEMX-3 

■ MX 

■ EMX 

■ ZMX 

□ MCA (ring) 

■ MCA (open) DOx-MX 


1 0-70 

13 

~ 0.60 

a> 

o 

§ 0-50 

O 

c ~ 0.40 

o 

C 05 

2 3 0.30 


0.20 

, 0.10 
0.00 




i 

i 

















| 

1 







jjj§ 



1 



•A' 








, 





r .. 

k v 1 




■■■■ 








ssa 

*■ # V *• ■» x 

FE 

03+Filter 

Plai 

PE 

NaOCI+NH3 

nt 1 

FE 

NaOCI+Filter 

PE 

NaOCI+NH3 

Plant 2 

DS/max 

NaOCI+NH3 


Sample Sites 


61 
















































VOCs. Although methyl tertiary butyl ether (MtBE) is not a DBP, it is a VOC that was 
included in this study. In January 2001, 0.3 jug/L of MtBE was detected in the raw water sample. 
The same level of MtBE was detected in the treated waters at plant 2, whereas a somewhat lower 
level (i.e., 0.2 pg/L) was detected at plant 1. In other research, ozone has been shown to destroy 
(at least in part) MtBE (Liang et al., 1999). If the decrease in MtBE at plant 1 was real, this 
could have been due to ozonation. 

Methyl ethyl ketone (MEK) is also a VOC. In addition, it was detected after ozonation at 
plant 1 in July 2001. Non-halogenated ketones can be formed by ozone (Glaze et al., 1989). 
MEK was not detected downstream of the ozone contactor effluent (with an MRL of 0.5 pg/L), 
perhaps due to biodegradation through the downstream treatment processes. 

Other Halogenated DBPs. A few additional, miscellaneous halogenated DBPs were also 
detected. UNC methods detected dichloroacetamide at 0.2 and 0.8 pg/L in finished water, 
respectively, from plant 1 and plant 2 in October 2000 (Table 12). Bromochloromethylacetate 
was also detected in finished waters from plant 1 at 0.1 pg/L (Table 12). In addition, 
broadscreen GC/MS analyses revealed the presence of chlorobenzene and tribromophenol (Table 
15) in finished waters from plant 1 (January 2001). None of these compounds were observed in 
the corresponding raw, untreated water. 

Non-Halogenated DBPs. The plant 1 ozonated drinking water offered one of the few 
times that cyanoformaldehyde was detected in the Nationwide DBP Occurrence Study. 
Cyanoformaldehyde had been first identified in a DBP study published in 1999 on ozonated 
drinking waters from a pilot plant (Richardson et al, 1999). Cyanoformaldehyde was found in 
the finished water at plant 1 in October 2000 at 0.2 pg/L, and its concentration remained steady 
at 0.2 pg/L in the distribution system (Table 12). Cyanoformaldehyde was also found in 
finished waters from plant 2 (which used chlorine disinfection) at 0.3 pg/L (October 2000). 
Dimethylglyoxal was also seen in ozone contactor effluent samples from plant 1 in both October 

2000 and July 2001, but was below detection in the finished water (plant effluent). In the July 

2001 sampling, it appeared to be removed by biological filtration, but in the October 2000 
sampling, its levels decreased between the filter effluent sampling and the plant effluent, 
indicating a possible reaction with the secondary chlorine-chloramine that was added following 
filtration. Broadscreen GC/MS analysis also revealed the presence of glyoxal and several non- 
halogenated carboxylic acids in samples from plant 1 in January 2001 (Table 15). Several of 
these carboxylic acids were also seen in the raw, untreated water, but those listed as DBPs in 
Table 15 represent those whose levels increased substantially (2-3X) in the treated waters vs. the 
raw, untreated waters. 


REFERENCES 

American Public Health Association (APHA). Standard Methods for the Examination of Water 
and Wastewater, 20th ed. APHA, American Water Works Association, and Water Environment 
Federation: Washington, DC (1998). 


62 


Bichsel, Y., and U. von Gunten. Formation of iodo-trihalomethanes during disinfection and 
oxidation of iodide-containing waters. Environmental Science & Technology 34(13):2784 
( 2000 ). 

Bolyard, M., P. S. Fair, and D. P. Hautman. Occurrence of chlorate in hypochlorite solutions 
used for drinking water disinfection. Environmental Science & Technology 26(8): 1663 (1992). 

Croue, J.-P., and D. A. Reckhow. Destruction of chlorination byproducts with sulfite. 

Environmental Science & Technology 23(11): 1412 (1989). 

Douville, C. J., and G. L. Amy. Influence of natural organic matter on bromate formation during 
ozonation of low-bromide drinking waters: a multi-level assessment of bromate. In Natural 
Organic Matter and Disinfection By-Products: Characterization and Control in Drinking Water 
(S.E. Barrett, S.W. Krasner, & G.L. Amy, eds.), pp. 282-298, American Chemical Society: 
Washington, D.C., 2000. 

Delcomyn, C. A., H. S. Weinberg, and P. C. Singer. Measurement of sub-pg/L levels of bromate 
in chlorinated drinking waters. Proceedings of the American Water Works Association Water 
Quality Technology Conference, American Water Works Association: Denver, CO, 2000. 

Glaze, W. H., M. Koga, D. Cancilla, K. Wang, M. J. McGuire, S. Liang, M. K. Davis, C. H. 

Tate, and E. M. Aieta. Evaluation of ozonation by-products from two California surface waters. 
Journal of the American Water Works Association 81(8):66 (1989). 

Hoigne, J., and H. Bader. The formation of trichloronitromethane (chloropicrin) and chloroform 
in a combined ozonation/chlorination treatment of drinking water. Water Research 22(3): 313 
(1988). 

Jacangelo, J. G., N. L. Patania, K. M. Reagan, E. M. Aieta, S. W. Krasner, and M. J. McGuire. 
Ozonation: assessing its role in the formation and control of disinfection by-products. Journal 
of the American Water Works Association 81 (8):74 (1989). 

Krasner, S. W., M. J. McGuire, J. G. Jacangelo, N. L. Patania, K. M. Reagan, and E. M. Aieta. 

The occurrence of disinfection by-products in U.S. drinking water. Journal of the American 
Water Works Association 81 (8):41 (1989). 

Krasner, S. W., J. M. Symons, G. E. Speitel, Jr., A. C. Diehl, C. J. Hwang, R. Xia, and S. E. 

Barrett. Effects of water quality parameters on DBP formation during chloramination. 

Proceedings of the American Water Works Association Annual Conference, Vol. D, American 
Water Works Association: Denver, CO, 1996. 

Kuo, C.-Y., H.-C. Wang, S. W. Krasner, and M. K. Davis. Ion-chromatographic determination 
of three short-chain carboxylic acids in ozonated drinking water. In Water Disinfection and 
Natural Organic Matter: Characterization and Control (R.A. Minear & G.L. Amy, eds.), pp. 
350-365, American Chemical Society: Washington, D.C., 1996. 


63 


Liang, S., L. S. Palencia, R. S. Yates, M. K. Davis, J.-M. Bruno, and R. L. Wolfe. Oxidation of 
MTBE by ozone and PEROXONE processes. Journal of the American Water Works Association 
91(6): 104 (1999). 

McKnight, A., and D. A. Reckhow. Reactions of ozonation by-products with chlorine and 
chloramines. Proceedings of the American Water Works Association Annual Conference (Water 
Research), American Water Works Association: Denver, CO, pp. 399-409, 1992. 

Reckhow, D. A., and P. C. Singer. The removal of organic halide precursors by preozonation 
and alum coagulation. Journal of the American Water Works Association 76(4): 151 (1984). 

Richardson, S. D., A. D. Thruston, Jr., T. V. Caughran, P. H. Chen, T. W. Collette, T. L. Floyd, 

K. M. Schenck, B. W. Lykins, Jr., G.-R. Sun, and G. Majetich. Identification of ozone 
disinfection byproducts in drinking water. Environmental Science & Technology 33:368 (1999). 

Richardson, S. D., A. D. Thruston, Jr., C. Rav-Acha, L. Groisman, I. Popilevsky, O. Juraev, V. 
Glezer, A. B. McKague, M. J. Plewa, and E. J. Wagner. Tribromopyrrole, brominated acids, and 
other disinfection byproducts produced by disinfection of drinking water rich in bromide. 
Environmental Science & Technology (submitted). 

Simpson, K.L. and K. P. Hayes. Drinking water disinfection by-products: an Australian 
perspective. Water Research 32(5): 1522 (1998). 

Symons, J. M., S. W. Krasner, L. A. Simms, and M. J. Sclimenti. Measurement of THM and 
precursor concentrations revisited: the effect of bromide ion. Journal of the American Water 
Works Association 85(1):51 (1993). 

van der Kooij, D., A. Visser, and W. A. M. Hijnen. Determining the concentration of easily 
assimilable organic carbon in drinking water. Journal of the American Water Works Association 
74(10):540 (1982). 

van der Kooij, D., and W. A. M. Hijnen. Substrate utilization by an oxalate consuming Spirillum 
species in relation to its growth in ozonated water. Applied Environmental Microbiology 47:551 
(1984). 

Volk, C. J., and M. W. LeChevallier. Effects of conventional treatment on AOC and BDOC 
levels. Journal of the American Water Works Association 94(6): 112 (2002). 

Xie, Y., and D. A. Reckhow. Hydrolysis and dehalogenation of trihaloacetaldehydes. In 
Disinfection By-Products in Water Treatment: The Chemistry of Their Formation and Control 
(R.A. Minear & G.L. Amy, eds.), pp. 283-291, CRC Lewis Publishers: Boca Raton, FL, 1996. 


64 


EPA REGION 6: PLANTS 11 AND 12 


Plant Operations and Sampling 

Plant 11 treated water from a river in EPA Region 6 (Figure 1) and plant 12 treated water 
from another river basin and lake in EPA Region 6. On March 26, 2001, September 10, 2001, 
November 5 or 15, 2001, and February 11 or 12, 2002, plants 11 and 12 were sampled. 

Plant 11 operated a chlorine dioxide plant (Figure 2): 

• Ferric sulfate [Fe 2 (S 04 ) 3 ] and cationic polymer were used for coagulation. 

• There was up-flow solids contact flocculation/clarification and 

dual-media filtration. 

• The disinfection strategy used a combination of free chlorine and chlorine dioxide to achieve 
disinfection requirements through the plant clearwell. 

• In March 2001, chlorine dioxide was only added post-filtration, in September 2001 and 
February 2002 chlorine dioxide was added to the clarified water and post-filtration, and in 
November 2001 chlorine dioxide was added before the clarifier and after the filters (after the 
sampling point for the clearwell influent). 

• The free chlorine residual was quenched with ammonia to form a chloramine residual prior to 
the storage tank and distribution. 

At plant 12 (Figure 3): 

• Alum was used for coagulation. 

• There was dual-media filtration. (They were in the process of scrapping the granular 
activated carbon [GAC] filter media and going back to dual media.) 

• The disinfection strategy used a combination of chlorine and ammonia to form chloramines. 

In February 2002, they used chlorine dioxide during pre-treatment. (They did not use 

chlorine dioxide as part of their treatment process in March, September, and November 

2001 .) 

Plant 11 was sampled at the following locations: 

(1) raw water 

(2) filter influent 

(3) filter effluent or clearwell influent 

(4) clearwell effluent (not sampled in November 2001 and February 2002) 

(5) the plant effluent 

In addition, the distribution system was sampled at two locations, one representing an average 
detention time and the other representing a maximum detention time. Furthermore, plant 
effluent was collected, and simulated distribution system (SDS) testing conducted with a 24- and 
a 48-hr holding time to represent the average and maximum detention times, respectively, in 
March 2001, September 2001, and February 2002. In November 2001, the SDS tests were 
conducted with holding times of 36 and 72 hr, respectively. 

However, the plant 11 SDS samples that were shipped on September 12, 2001 were not 
delivered to Metropolitan Water District of Southern California (MWDSC) until September 17, 

2001, since Federal Express could not use air delivery at that time. Because the samples were 


65 


not kept cold for that entire period of time, the SDS samples for the September 2001 sampling 
represent a test of the long-term stability of the DBPs when held at room temperature. 

Figure 1. EPA Region 6 



New-Mexico - Oklahoma - Arkansas - Louisiana - Texas 


66 















Figure 2. Plant 11 schematic 



67 

































































































Figure 3. Plant 12 schematic 



Distribution 


Plant 12 was sampled at the following locations: 

(1) raw water, 

(2) after pre-treatment, 

(3) filter influent, 

(4) filter effluent, 

(5) and the plant effluent. 

In addition, the distribution system was sampled at two locations, one representing an average 
detention time and the other representing a maximum detention time. In March 2001, plant 
effluent was collected and SDS testing was conducted with a 18- and a 30-hr holding time to 
represent the average and maximum detention times, respectively. SDS testing was not 
performed in September 2001. In November 2001, the SDS tests were conducted with holding 
times of 24 and 48 hr, respectively. In February 2002, the SDS samples were held for less than 
one day (holding times are not available). On the day of sampling, information was collected on 
the operations at each plant (Tables 1-2). 


68 


















Table 1. Operational information at plant 11 


Parameter 

3/26/01 

9/10/01 

11/5/01 

2/11/02 

Plant flow (mgd) 

12.96 

37.4 

31.7 

28.8 

Fe2(S04)3 dose (mg/L) 

18.7 

7.6 

8.5 

10.4 

Polymer (coagulant aid) dose (mg/L) 

3.9 

2.7 

2.4 

7.1 

Polymer (filter aid) dose (mg/L) 

0.024 

0.048 

0.048 

0.048 

Chlorine dioxide dose before clarifier (mg/L as CIO 2) 

0 

0 

0.35 

0 

Chlorine dioxide dose at clarifier (mg/L as CIO 2) 

0 

0.35 

0 

0.25 

Chlorine dioxide dose post-filtration (mg/L as CIO 2) 

0.75 

0.5 

0.5 

0.5 

Chlorine dose at filter effluent (mg/L as CI2) 

4.5 

4.1 

4.1 

4.0 

Ammonia dose at clearwell effluent (mg/L as NH3-N) 

1.25 

1.15 

1.15 

0.86 


Table 2. Operational information at plant 12 


Parameter 

3/26/01 

9/10/01 

11/15/01 

2/12/02 

Plant flow (mgd) 

72 

64 

60 

60 

Coagulant dose used for pre-treatment (mg/L) 

0 

0 

0 

0 

Chlorine dioxide dose (mg/L as CIO 2) 

0 

0 

0 

1.0 

Potassium permanganate (KMn04) dose used for pre¬ 
treatment (mg/L) 

NA a 

1 

1.0 

1.0 

Chlorine dose after pre-treatment (mg/L as CI2) 

4.6 

6.0 

6.5 

5.0 

Ammonia dose after pre-treatment (mg/L as NH3-N) 

0.72 

1.5 

1.2 

0.82 

Aluminum sulfate dose used in sed. basins (mg/L) 

80 

95 

80 

80 

No. filters contained GAC, contained dual media 

8,9 

0, all 

0, 22 

0, 22 

Chlorine dose at filter effluent (mg/L as CI2) 

5.5 

4.8 

3.3 

2.4 

Ammonia dose at filter effluent (mg/L as NH3-N) 

0.71 

1.2 

0.61 

0.44 


a NA = Not available 


Water Quality 

On the day of sampling, information was collected on water quality at each plant 
(Tables 3-4). Additional data were collected for total organic carbon (TOC) and ultraviolet (UV) 
absorbance (Tables 5-6). At plant 12, the raw water equaled a blend from two lakes. The blend 
ratio changed from day to day. Water after pre-treatment equaled a blend of raw and pre-treated 
(KMn04) water. The detention time in the pre-sedimentation basin lead to a mixture of current 
and previous blends. Thus, the difference in water quality between the raw and pre-treated water 
at plant 12 represented, in part, changes in the blend ratio. 

At plant 12 in March 2001, September 2001, November 2001, and February 2002, the 
water after pre-treatment had 2-19 % less TOC than the raw water, and coagulation subsequently 
removed 21-40 % of the remaining TOC in the pre-treated water. The water after pre-treatment 
had a 13-28 % reduction in UV, and coagulation reduced the UV of the pre-treated water by an 
additional 38-54 %. At plant 11 in March 2001, September 2001, November 2001, and February 
2002, coagulation and filtration cumulatively removed 17-30 % of the TOC and reduced the UV 
by 23-65 %. 


69 































Table 3. Water quality information at plant 11 



pH 

Temperature (°C) 

Disinfectant Residual 2 (mg/L) 

Location 

3/26/01 

9/10/01 

11/5/01 

2/11/02 

3/26/01 

9/10/01 

11/5/01 

2/11/02 

3/26/01 

9/10/01 

11/5/01 

2/11/02 

Raw water 

8.14 

8.12 

8.33 

NA 

19.2 

26.2 

21.2 

11.2 

— 

— 

— 

— 

Filter influent 

7.54 

7.86 

8.13 

7.98 

19.0 

26.8 

21.3 

11.6 

— 

0.31 

— 

— 

Filter eff. or clear, inf. 

7.65 

7.38 

7.47 

7.49 

19.0 

26.4 

22.3 

11.4 

— 

3.3 

— 

0.17/ 

3.7 

Clearwell effluent 

7.30 

7.48 

NS° 

NS 

18.0 

27.8 

NS 

NS 

0.31/ 

2.5 

2.6 

NS 

NS 

Plant effluent 

7.40 

7.52 

7.52 

7.47 

18.2 

24.8 

21.9 

11.4 

0.02/ 

2.7 

3.0 

0.10/ 

2.9 

0.13/ 

3.2 

Dist. system/average 

7.52 

7.62 

7.62 

7.62 

19.3 

27.6 

23.3 

12.1 

2.6 

2.6 

2.7 

2.7 

Dist. system/maximum 

7.44 

7.58 

7.68 

7.68 

20.2 

27.8 

22.9 

12.3 

2.5 

2.5 

2.4 

2.5 

SDS/average 

7.63 

7.53 

7.52 

7.53 

20.0 

26.0 

21.4 

13.9 

2.7 

2.4 

2.5 

2.8 

SDS/maximum 

7.52 

7.57 

7.56 

7.52 

18.1 

25.8 

21.6 

14.1 

2.5 

2.3 

2.2 

2.7 


“Chlorine dioxide residuals (values shown in bold) in clearwell effluent and plant effluent in March 2001, in filter influent in September 2001, in 
plant effluent in November 2001, and in clearwell influent and in plant effluent in February 2002; chlorine residuals (values shown in italics) in 
clearwell influent in September 2001 and in February 2002; chloramine residuals at other locations. 
b NS = Not sampled 


Table 4. Water quality information at plant 12 




dH 

Temperature (°C) 

Disinfectant Residuaf (mg/L) 

Location 

3/26/01 

9/10/01 

11/15/01 

2/12/02 

3/26/01 

9/10/01 

11/15/01 

2/12/02 

3/26/01 

9/10/01 

11/15/01 

2/12/02 

Raw water 

8.3 

7.7 

7.6 

7.8 

20.9 

28 

23.6 

16 

— 

— 

— 

— 

After pre-treatment 

8.4 

7.8 

8.0 

7.8 

19.9 

28 

23.4 

14 

— 

— 

— 

0.15 

Filter influent 

8.8 

8.3 

8.1 

8.4 

19.0 

27 

24.1 

17 

2.1 

1.6 

2.3 

1.7 

Filter effluent 

8.2 

7.6 

NA 

8.1 

20.8 

27 

23.1 

16 

1.6 

4.8 

2.1 

1.4 

Plant effluent 

8.1 

7.6 

8.3 

7.6 

20.8 

27 

23.4 

14 

4.9 

4.7 

4.3 

4.6 

Dist. system/average 

7.8 

7.7 

NA 

7.4 

15.4 

26 

NA 

16 

3.6 

3.2 

NA 

NA 

Dist. system/maximum 

7.7 

7.7 

NA 

7.4 

21.3 

25 

NA 

18 

2.2 

2.6 

NA 

NA 

SDS/average 

NA 

NS° 

7.3 

7.4 

NA 

NS 

25 

16 

NA 

NS 

3.4 

2.7 

SDS/maximum 

NA 

NS 

7.3 

7.4 

NA 

NS 

25 

18 

NA 

NS 

2.8 

2.4 


“Chlorine dioxide residual (value shown in bold) at pre-treatment sample location in February 2002; chloramine residua 
b NS = Not sampled 


s at other 


ocations. 


70 

















































Table 5. TOC and UV removal at plant 11 


Location 

TOC 

(mq/L) 

UV a 

(cm’ 1 ) 

SUVA b 

(L/mq-m) 

Remova 

/Unit (%) 

Removal/Cumulative (%) 

TOC 

UV 

TOC 

UV 

03/26/2001 








Raw 

5.66 

0.137 

2.42 

— 

— 

— 

_ _ 

Filter Inf. 

4.08 

0.083 

2.03 

28% 

39% 

28% 

39% 

Filter Eff. 

4.24 

0.089 

2.10 

-3.9% 

-7.2% 

25% 

35% 

09/10/2001 








Raw 

3.51 

0.079 

2.25 

— 

_ 

... 

... 

Filter Inf. 

3.24 

0.069 

2.13 

7.7% 

13% 

7.7% 

13% 

Clearwell Inf. 

2.89 

0.044 

1.52 

11% 

36% 

18% 

44% 

11/5/2001 








Raw 

4.68 

0.115 

2.46 

_ 

_ 

... 

_ _ 

Filter Inf. 

4.0 

0.094 

2.35 

15% 

18% 

15% 

18% 

Clearwell Inf. 

3.87 

0.088 

2.27 

3.3% 

6.4% 

17% 

23% 

02/11/2002 








Raw 

4.26 

0.108 

2.54 

— 

— 

— 

— 

Filter Inf. 

3.25 

0.055 

1.69 

24% 

49% 

24% 

49% 

Clearwell Inf. 

3.0 

0.038 

1.27 

7.7% 

31% 

30% 

65% 


a UV = Ultraviolet absorbance reported in units of "inverse centimeters" (APHA, 1998) 
b SUVA (L/mg-m) = Specific ultraviolet absorbance = 100*UV (cm'^/DOC (mg/L) or UV (m'^/DOC (mg/L), 
where DOC = dissolved organic carbon, which typically = 90-95% TOC (used TOC values in calculating SUVA) 
(e.g., UV = 0.137/cm = 0.137/(0.01 m) = 13.7/m, DOC = 5.66 mg/L, SUVA = (13.7 m' 1 )/(5.66 mg/L) = 2.42 L/mg-m) 


Table 6. TOC and UV removal at plant 12 


Location 

TOC 

(mg/L) 

UV 3 

(cm 1 ) 

SUVA b 

(L/mq-m) 

Removal/Unit (%) 

Removal/Cumulative (%) 

TOC 

UV 

TOC 

UV 

03/26/2001 








Raw 

6.72 

0.184 

2.74 

_ 

_ 

— 

— 

After Pre-Treat. 

6.12 

0.160 

2.61 

8.9% 

13% 

8.9% 

13% 

Filter Inf. 

4.48 

0.095 

2.12 

27% 

41% 

33% 

48% 

Filter Eff. 

4.52 

0.086 

1.90 

-0.9% 

9.5% 

33% 

53% 

09/10/2001 








Raw 

7.52 

0.273 

3.63 

— 

— 

— 

— 

After Pre-Treat. 

6.20 

0.196 

3.16 

18% 

28% 

18% 

28% 

Filter Inf. 

3.70 

0.091 

2.46 

40% 

54% 

51% 

67% 

Filter Eff. 

3.80 

0.089 

2.34 

-2.7% 

2.2% 

49% 

67% 

11/15/2001 








Raw 

7.01 

0.233 

3.32 

— 

— 

— 

— 

After Pre-Treat. 

5.71 

0.188 

3.29 

19% 

19% 

19% 

m 

Filter Inf. 

4.51 

0.117 

2.59 

21% 

38% 

36% 

50% 

Filter Eff. 

4.42 

0.115 

2.60 

2.0% 

1.7% 

37% 

51% 

02/12/2002 








Raw 

5.33 

0.176 

3.30 

— 

— 

— 

— 

After Pre-Treat. 

5.24 

0.129 

2.46 

1.7% 

27% 

1.7% 

27% 

Filter Inf. 

3.30 

0.070 

2.12 

37% 

46% 

38% 

60% 

Filter Eff. 

3.21 

0.069 

2.15 

2.7% 

1.4% 

40% 

61% 


a UV = Ultraviolet absorbance reported in units of "inverse centimeters" (APHA, 1998) 
b SUVA (L/mg-m) = Specific ultraviolet absorbance = 100*UV (cm'^/DOC (mg/L) or UV (m _1 )/DOC (mg/L), 
where DOC = dissolved organic carbon, which typically = 90-95% TOC (used TOC values in calculating SUVA) 
(e.g., UV = 0.184/cm = 0.184/(0.01 m) = 18.4/m, DOC = 6.72 mg/L, SUVA = (18.4 m _1 )/(6.72 mg/L) = 2.74 L/mg-m) 


71 

























































Table 7 shows the values of miscellaneous other water quality parameters in the raw 
waters at the two EPA Region 6 plants. 

Table 7. Miscellaneous water quality parameters in raw water at the EPA Region 6 plants 
Plant 11 Plant 12 


Date 

Bromide 

(mg/L) 

Alkalinity 

(mg/L) 

Ammonia 
(mg/L as N) 

03/26/2001 

0.18 

121 

ND 

09/10/2001 

0.21 

117 

0.15 

11/5/2001 

0.16 

133 

ND 

02/11/2002 

0.18 

153 

ND 


Date 

Bromide 

(mg/L) 

Alkalinity 

(mg/L) 

Ammonia 
(mg/L as N) 

03/26/2001 

0.25 

123 

ND 

09/10/2001 

0.02 

54 

0.04 

11/15/2001 

0.15 

70 

ND 

02/12/2002 3 

0.33 

111 

ND 


a Bromide sampled at pre-treatment sample 
location in February 2002 


Both EPA Region 6 plants treated waters high in TOC, bromide, and alkalinity in March 
2001, November 2001, and February 2002 (Tables 5-7, Figure 4). However, in September 2001, 
the water qualities were quite different (Table 5-7, Figure 5): the TOC at plant 11 was lower, 
whereas the bromide and alkalinity at plant 12 was lower. 

Figure 4 Figure 5 


Comparison of Raw Water Quality at 
Plants 11 and 12: 3/26/01 



Comparison of Raw Water Quality at 
Plants 11 and 12: 9/10/01 


c 

o 

o 



At plant 12, the bromide and alkalinity on September 10, 2001 were significantly lower 
than on March 26, 2001, whereas the TOC was only slightly higher. This could either reflect a 
different blend of source waters on the two sampling dates or some seasonal variation in water 
quality. For example, a storm event can result in an increase in TOC due to runoff and a dilution 
of inorganic parameters such as bromide and alkalinity. 

DBPs 


Oxyhalides. Tables 8-9 show the formation of oxyhalides at the two plants. Chlorine 
dioxide will typically not react with bromide to form bromate, as was observed at plant 11 (Table 
8 ) and plant 12 in February 2002 (Table 9). 


72 









































































































































Table 8. Oxyhaiide formation at plant 11 


Location 

Bromate 3 

(MQ/L) 

Chlorite 3 

(Mg/L) 

Chlorate 3 

(pg/L) 

CI0 2 7CI0 2 b 

% 

03/26/2001 





Filter Eff. 

ND 

ND 

ND 

— 

Clearwell Eff. 

ND 

639 

244 

85% 

09/10/2001 





Clearwell Inf. 

ND 

399 

94 

47% 

Clearwell Eff. 

ND 

406 

160 

48% 

11/5/2001 





Filter Inf. 

ND 

238 

47 

68% 

Clearwell Inf. 

ND 

202 

47 

58% 

Plant Eff. 

ND 

478 

159 

56% 

02/11/2002 





Filter Inf. 

ND 

135 

36 

54% 

Clearwell Inf. 

ND 

212 

289 

28% 

Plant Eff. 

ND 

420 

167 

56% 


Reporting detection level for bromate = 3 pg/L and for chlorate and chlorite = 5 pg/L 
b Chlorine dioxide dose in March 2001 = 0.75 mg/L 

Chlorine dioxide dose in September 2001 = 0.35 mg/L at clarifier and 0.5 mg/L at post 
Chlorine dioxide dose in November 2001 = 0.35 mg/L before clarifier and 0.5 mg/L at post 
Chlorine dioxide dose in February 2002 = 0.25 mg/L at clarifier and 0.5 mg/L at post 


Table 9. Oxyhaiide formation at plant 12 


Location 

Bromate 

(pg/L) 

Chlorite 

(pg/L) 

Chlorate 

(pg/L) 

CI0 2 7CI0 2 a 

% 

03/26/2001 





After Pre-Treat. 

ND 

ND 

8.6 

— 

Filter Inf. 

ND 

ND 

30 

— 

Filter Eff. 

ND 

ND 

32 

— 

09/10/2001 





After Pre-Treat. 

ND 

ND 

ND 

— 

Filter Inf. 

ND 

ND 

ND 

— 

Filter Eff. 

ND 

ND 

ND 

— 

11/15/2001 





After Pre-Treat. 

ND 

ND 

ND 

— 

Filter Inf. 

ND 

ND 

ND 

— 

Filter Eff. 

ND 

ND 

ND 

— 

02/12/2002 





After Pre-Treat. 

ND 

900 

94 

90% 

Filter Inf. 

ND 

648 

182 

65% 

Filter Eff. 

ND 

634 

169 

63% 


a Chlorine dioxide dose in February 2002 - 1.0 mg/L 


73 










































It has been reported that during water treatment, approximately 50-70 % of the chlorine 
dioxide (CIO 2 ) reacted will immediately appear as chlorite (CIO 2 ’) and the remainder as chloride 
(Aieta and Berg, 1986). At plant 11, a similar percentage was observed in November 2001 and 
for most of the samples collected in February 2002, whereas a somewhat higher amount of 
chlorite was detected in March 2001 and a somewhat lower level was detected in September 
2001 (Table 8). Likewise, a similar percentage to that reported by Aieta and Berg (1986) was 
observed for most of the samples collected in February 2002 at plant 12 (Table 9). 

Because chlorine dioxide was not used at plant 12 on March 26, 2001, September 10, 
2001, or November 15, 2001, no chlorite was detected (Table 9). However, a very low amount 
of chlorate was found in the water in March 2001, even before the addition of chlorine (Table 9). 
In other research, low levels of chlorate have been detected in raw water samples (Bolyard et al., 
1992). 


Organic DBPs. Tables 10 and 11 (3/26/01), Tables 13 and 14 (9/10/01), Tables 19 and 
20 (11/5/01 and 11/15/01), and Tables 22 and 23 (2/11/02 and 2/12/02) show results for the 
halogenated organic DBPs that were analyzed by MWDSC. Table 12 (3/26/01 [plant 11] and 
Table 21 (11/15/01 [plant 12]) shows results from broadscreen DBP analyses conducted at the 
U.S. Environmental Protection Agency (USEPA). Tables 15 and 16 (9/10/01), and Tables 24 
and 25 (2/11/02 and 2/12/02) show results for additional target DBPs that were analyzed for at 
the University of North Carolina (UNC). Tables 17 and 18 (9/10/01), and Tables 26 and 27 
(2/11/02 and 2/12/02) show results for halogenated fiiranones that were analyzed at UNC. 


Summary of tables for organic DBPs 


DBP Analyses (Laboratory) 

3/26/01 

9/10/01 

11/5/01 and 
11/15/01 

2 /11/02 and 
2 /12/02 

Halogenated organic DBPs 
(MWDSC) 

Tables 10- 
11 

Tables 13-14 

Tables 19-20 

Tables 22-23 

Additional target DBPs (UNC) 


Tables 15-16 


Tables 24-25 

Halogenated furanones (UNC) 


Tables 17-18 


Table 26-27 

Broadscreen analysis (USEPA) 

Table 12 a 


Table 21° 



a Plant 11 
b Plant 12 


74 












Table 10. DBP results at plant 11 (3/26/01) 


03/26/2001 

MRL a 

P 

ant 11 b 

Compound 

hh /l 

Raw 

Filt Eff 

Clearwell 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Halomethanes 










Chloromethane 

0.15 

ND C 


ND 

ND 

ND 


0.35 


Bromomethane 

■. ;:n 

ND 


ND 

ND 

ND 


ND 


Bromochloromethane 

0.14 

ND 


ND 

ND 

ND 


ND 


Dibromomethane 

0.11 

ND 


ND 

ND 

ND 


ND 


Chloroform d 

0.1 

ND 

0.2 

8 

6 

6 

6 

7 

7 

Bromodichloromethane d 

0.1 

ND 

0.4 

19 

15 

15 

17 

17 

17 

Dibromochloromethane d 

0.10 

ND 

0.4 

23 

19 

18 

21 

20 

20 

Bromoform d 

0.12 

ND 

ND 

7 

6 

6 

5 

6 

6 

THM4® 


ND 

1.0 

57 

46 

45 

49 

50 

50 

Dichloroiodomethane 

0.2 

ND 

ND 

0.3 

ND 

0.2 

ND 

ND 

ND 

Bromochloroiodomethane 

0.20 

ND 

ND 

0.3 

ND 

0.2 

ND 

0.2 

ND 

Dibromoiodomethane 

0.60 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.51 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.56 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.54 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 

ND 


0.2 

0.15 

ND 


ND 


T ribromochloromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 










Monochloroacetic acid d 

2 


ND 

ND 

ND 

ND 


2.7 


Monobromoacetic acid d 

1 


ND 

ND 

ND 

ND 


ND 


Dichloroacetic acid d 

1 


ND 

10 

9.7 

11 


12 


Bromochloroacetic acid d 

1 


ND 

12 

11 

13 


13 


Dibromoacetic acicf 1 

1 


ND 

8.7 

8.1 

8.9 


9.2 


Trichloroacetic acid d 

1 


ND 

4.5 

3.8 

5.1 


5.4 


Bromodichloroacetic acid 

1 


ND 

10 

9.0 

11 


11 


Dibromochloroacetic acid 

1 


ND 

8.8 

7.5 

8.9 


9.2 


Tribromoacetic acid 

2 


ND 

ND 

ND 

ND 


ND 


HAA5 f 



ND 

23 

22 

25 


29 


HAA9 9 



ND 

54 

49 

58 


63 


DXAA h 



ND 

31 

29 

33 


34 


TXAA' 



ND 

23 

20 

25 


26 


Haloacetonitriles 










Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

I" 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.10 

ND 

ND 

0.3 

2 

2 

2 

2 

2 

Bromochloroacetonitrile d 

0.1 

ND 

ND 

0.4 

3 

3 

3 

3 

3 

Dibromoacetonitrile d 

0.17 

ND 

ND 

0.6 

3 

4 

4 

4 

4 

T richloroacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetaldehvdes 










Dichloroacetaldehvde 

0.16 

ND 

ND 

1 

0.4 

0.8 

1 

0.8 

1 

Bromochloroacetaldehvde 

0.1 

0.1 

ND 

0.6 

0.3 

0.4 

0.8 

0.4 

0.4 

Chloral hvdrate d 

0.1 

0.2 

ND 

0.3 

0.5 

0.6 

1 

0.7 

0.6 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

0.5 

ND 

ND 


75 



























































Table 10 (continued) 


03/26/2001 

MRL a 

pq/L 

P 

ant 11 b 

Compound 

Raw 

Filt Eff 

Clearwell 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloketones 










ChloroDroDanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dichloropropanone d 

0.11 

ND 

ND 

1 

0.3 

0.4 

0.3 

0.4 

0.5 

1,3-Dichloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

0.5 

ND 

ND 

1,1-Dibromoprooanone 

3 

ND 


ND 

ND 

ND 


ND 


1,3-Dibromopropanone 

3 

ND 


ND 

ND 

ND 


ND 


1,1,1 -T richloropropanone d 

0.10 

ND 

ND 

ND 

0.8 

0.4 

1 

0.6 

0.4 

1,1,3-T richloropropanone 

0.11 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

3 

ND 


ND 

<1* 

ND 


ND 


1,1,1 -T ribromopropanone 

3 

ND 


ND 

ND 

ND 


ND 


1,1,3-Tribromopropanone 

3 

ND 


ND 

ND 

ND 


ND 


1,1,3,3-Tetrachloropropanone 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1.1.3-T etrachloroDroDanone 

3 

ND 


ND 

ND 

ND 


ND 


1,1,3,3-Tetrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 










Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

3 

ND 


ND 

<1 

<1 


<1 


Bromochloronitromethane 

3 

ND 


ND 

<1 

<1 


<1 


Dibromonitromethane 

0.12 

ND 

ND 

0.2 

0.4 

ND 

0.2 

ND 

ND 

Chloropicrin d 

0.1 

ND 

ND 

ND 

ND 

0.4 

0.1 

0.2 

0.4 

Miscellaneous Compounds 










Methyl ethyl ketone 

1.90 

ND 


ND 

ND 

ND 


ND 


Methvl tertiary butvl ether 

0.16 

ND 


ND 

ND 

ND 


ND 


Benzyl chloride 

2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


a MRL = Minimum reporting level, which equals method detection limit (MDL) 
or lowest calibration standard or concentration of blank 

b Plant 11 sampled at (1) raw water, (2) filter effluent, (3) clearwell effluent, (4) plant effluent, 
distribution system (DS) at (5) average and (6) maximum detention times, and 
SDS testing of plant effluent at (7) average and (8) maximum detention times 
C ND = Not detected at or above MRL 

d DBP in the Information Collection Rule (ICR) (note: some utilities collected data for all 9 
haloacetic acids for the ICR, but monitoring for only 6 haloacetic acids was required) 
e THM4 = Sum of 4 THMs (chloroform, bromodichloromethane, dibromochloromethane, bromoform) 
f HAA5 = Sum of 5 haloacetic acids (monochloro-, monobromo-, dichloro-, dibromo-, trichloroacetic acid) 
9 HAA9 = Sum of 9 haloacetic acids 

h DXAA = Sum of dihaloacetic acids (dichloro-, bromochloro-, dibromoacetic acid) 

'TXAA = Sum of trihaloacetic acids (trichloro-, bromodichloro-, dibromochoro-, tribromoacetic acid) 

J <1: Concentration less than lowest calibration standard (i.e., 1 pg/L) 


76 






































Table 11. DBP results at plant 12 (3/26/01) 


03/26/2001 

MRL“ 

Plant 1? 

Compound 

Ud/L 

Raw 

Pre-Treat 

Filt Inf 

Filt Eff 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Halomethanes 











Chloromethane 

0.15 

ND C 


ND 


ND 

ND 


ND 


Bromomethane 

0.20 

ND 


ND 


ND 

ND 


ND 


Bromochloromethane 

0.14 

ND 


ND 


ND 

ND 


ND 


Dibromomethane 

0.11 

ND 


ND 


ND 

ND 


ND 


Chloroform d 

0.1 

ND 

0.2 

6 

5 

5 

6 

6 

5 

7 

Bromodichloromethane d 

0.1 

ND 

ND 

11 

10 

11 

14 

17 

12 

15 

Dibromochloromethane d 

0.10 

ND 

0.4 

8 

8 

10 

18 

30 

12 

16 

Bromoform d 

0,12 

ND 

ND 

5 

7 

8 

14 

31 

9 

11 

THM4 e 


ND 

0.6 

30 

30 

34 

52 

84 

38 

49 

Dichloroiodomethane 

0.2 

ND 

ND 

3 

NR 1 

4 

4 

NR 

4 

NR 

Bromochloroiodomethane 

0.20 

ND 

ND 

3 

NR 

3 

6 

NR 

3 

2 

Dibromoiodomethane 

0.60 

ND 

ND 

2 

2 

3 

7 

0.8 

4 

4 

Chlorodiiodomethane 

0.51 

ND 

ND 

2 

1 

2 

3 

ND 

3 

2 

Bromodiiodomethane 

0,50 

ND 

ND 

ND 

ND 

0.3 

1 

ND 

0.4 

ND 

Iodoform 

0.54 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 

ND 


ND 


ND 

ND 


ND 


Tribromochloromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 











Monochloroacetic acid d 

2 


ND 

ND 

ND 

ND 

ND 


2.0 


Monobromoacetic acid d 

1 


ND 

ND 

ND 

ND 

ND 


ND 


Dichloroacetic acid d 

1 


ND 

11 

12 

14 

12 


14 


Bromochloroacetic acid d 

1 


ND 

10 

12 

15 

15 


14 


Dibromoacetic acid d 

1 


ND 

6.9 

7.7 

12 

14 


12 


Trichloroacetic acid d 

1 


ND 

2.4 

4.1 

5.1 

3.5 


5.1 


Bromodichloroacetic acid 

1 


ND 

2.1 

4.8 

6.0 

5.2 


5.8 


Dibromochloroacetic acid 

1 


ND 

1.5 

3.4 

3.9 

4.1 


3.7 


Tribromoacetic acid 

2 


ND 

ND 

ND 

ND 

ND 


ND 


HAA5 f 



ND 

20 

24 

31 

30 


33 


HAA9 9 



ND 

34 

44 

56 

54 


57 


DXAA h 



ND 

28 

32 

41 

41 


40 


TXA A 



ND 

6.0 

12 

15 

13 


15 


Haloacetonitriles 











Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.10 

ND 

ND 

0.8 

0.7 

1 

2 

1 

2 

2 

Bromochloroacetonitrile d 

0.1 

ND 

ND 

1 

1 

2 

2 

3 

2 

2 

Dibromoacetonitrile d 

0.17 

ND 

ND 

0.6 

0.6 

1 

3 

4 

2 

2 

Trichloroacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetaldehvdes 











Dichloroacetaldehvde 

0,10 

ND 

ND 

1 

0.5 

0.6 

0.6 

0.3 

0.7 

QJ 

Bromochloroacetaldehvde 

0.1 

ND 

ND 

0.9 

0.4 

0.6 

0.9 

0.6 

0.8 

0.9 

Chloral hydrate d 

0.1 

0.1 

ND 

0.8 

0.2 

0.2 

0.4 

0.2 

0.3 

0.3 

T ribromoacetaldehyde 

0.1 

ND 

ND 

0.6 

ND 

0.2 

0.2 

0.2 

0.3 

0.2 


77 



























































Table 11 (continued) 


03/26/2001 

"mrl* 

Plant 12° 

Compound 

pg/L 

Raw 

Pre-T reat 

Filt Inf 

Filt Eff 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloketones 











Chloropropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dichloropropanone d 

0.11 

ND 

ND 

0.4 

0.3 

0.3 

ND 

ND 

0.3 

0.3 

1,3-Dichloropropanone 

0.10 

ND 

ND 

0.3 

ND 

ND 

ND 

ND 

ND 

ND 

1.1-Dibromopropanone 

3 

ND 


ND 


ND 

ND 


ND 


1.3-Dibromopropanone 

3 

ND 


ND 


ND 

ND 


ND 


1,1,1-Trichloropropanone d 

0.10 

ND 

ND 

0.3 

0.2 

0.3 

0.2 

ND 

0.3 

0.3 

1,1,3-T richloropropanone 

0.11 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

3 

ND 


<1 j 


<1 

ND 


<1 


1,1,1-Tribromopropanone 

3 

ND 


ND 


ND 

ND 


ND 


1,1,3-T ribromopropanone 

3 

ND 


ND 


ND 

ND 


ND 


1,1,3,3-Tetrachloropropanone 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-Tetrachloropropanone 

3 

ND 


ND 


ND 

ND 


ND 


1,1,3,3-Tetrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 











Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

3 

ND 


<1 


<1 

<1 


<1 


Bromochloronitromethane 

3 

ND 


<1 


<1 

<1 


<1 


Dibromonitromethane 

0.12 

ND 

ND 

0.1 

ND 

0.3 

0.4 

0.8 

0.3 

0.2 

Chloropicrin d 

0.1 

ND 

ND 

0.1 

0.1 

0.2 

0.2 

0.1 

0.2 

0.4 

Miscellaneous Compounds 











Methyl ethyl ketone 

1.90 

ND 


ND 


ND 

ND 


ND 


Methyl tertiary butyl ether 

0.16 

ND 


ND 


ND 

ND 


ND 


Benzyl chloride 

2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


k Plant 12 sampled at (1) raw water, (2) after pre-treatment, (3) filter influent, (4) filter effluent, 

(5) plant effluent, DS at (6) average and (7) maximum detention times, and 
SDS testing of plant effluent at (8) average and (9) maximum detention times 

NR = Not reported, due to interference problem on gas chromatograph or to problem with quality assurance 


78 







































Table 12. Occurrence of other DBPs a at plant 11: plant effluent (3/26/01) 


Halomethanes 

Dibromochloromethane b 

Bromoform 

Dichloroiodomethane 

Bromochloroiodomethane 

Dibromoiodomethane 


Haloketones 

1.1 -Dichloropropanone 

1.1.1 -Trichloropropanone 

1,1,3 - Trichloropropanone 

1 -Bromo-1,1 - dichloropropanone 

1, l-Dibromo-3-chloropropanone 

1.1.3- Tribromopropanone 

1 - Bromo-1,3,3 - trichloropropanone 

1.3- Dibromo-l ,3-dichloropropanone 

1.1.3- Tribromo-3-chloropropanone 

1.1.3.3- Tetrabromopropanone 

Haloacids 

Dichloroacetic acid 

Bromochloroacetic acid 

Dibromoacetic acid 
Bromodichloroacetic acid 


Tribromoacetic acid 

2.2- Dibromopropanoic acid 
Dibromochloropropanoic aeid c 

3.3- Dibromopropenoic acid 
Bromochloro-4-oxopentanoic aeid c 

3.3- Dibromo-4-oxopentanoic acid 
Bromoheptanoic acid 0 
Bromochloroheptanoic acid 0 (2 

isomers) 

Dibromoheptanoic acid 0 
Bromochlorononanoic acid 0 


Haloacetonitriles 

Bromochloroacetonitrile 

Dibromoacetonitrile 

Dibromochloroacetonitrile 

Tribromoacetonitrile 


Haloaldehydes 

Bromochloroacetaldehyde 

Dibromoacetaldehyde 

Bromodichloroacetaldehyde 

2-Bromo-2-methylpropanal 

2 - (4- Chloro- 2 - methy lphenoxy) - 
propanoic acid 


Halonitromethanes 

Dichloronitromethane 

cis-2-Bromo-3-methylbutenedioic acid 


Non-halogenated DBPs 



Octadecanoic acid 


a DBPs detected by broadscreen gas chromatography/mass spectrometry (GC/MS) technique. 
b Compounds listed in italics were confirmed through the analysis of authentic standards; 
haloacids and non-halogenated carboxylic acids identified as their methyl esters. 
c Exaet isomer not known 


79 
















Table 13. DBP results at plant 11 (9/10/01) 


09/10/2001 

MRL a 

Plant 11 b 

Compound 

Ud/L 

Raw 

Filt Eff 

Clearwell 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Halomethanes 










Chloromethane 

0.2 

ND C 


ND 

ND 

ND 


ND 


Bromomethane 

0.2 

ND 


ND 

ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 


ND 

ND 

ND 


ND 


Dibromomethane 

0.5 

ND 


ND 

ND 

ND 


ND 


Chloroform d 

0.1 

ND 

1 

3 

2 

4 

4 

1 

1 

Bromodichloromethane d 

0.1 

ND 

6 

16 

17 

21 

22 

16 

44 

Dibromochloromethane d 

0.1 

ND 

10 

24 

24 

26 

27 

24 

16 

Bromoform d 

0.1 

ND 

2 

6 

6 

8 

9 

5 

8 

THM4 e 


ND 

19 

49 

49 

59 

62 

46 

69 

Dichloroiodomethane 

0.5 

ND 

2 

1 

2 

0.9 

0.7 

ND 

ND 

Bromochloroiodomethane 

0.5 

ND 

ND 

0.8 

0.7 

ND 

ND 

ND 

ND 

Dibromoiodomethane 

0.25 

ND 

ND 

0.4 

0.4 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

0.3 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0 2 

ND 


ND 

ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 










Monochloroacetic acid d 

2 


ND 

ND 

ND 

ND 




Monobromoacetic acid d 

1 


ND 

1.4 

1.4 

1.2 




Dichloroacetic acid d 

1 


3.2 

4.8 

4.7 

5.1 




Bromochloroacetic acid d 



5.1 

8.0 

7.8 

9.4 




Dibromoacetic acid d 



8.2 

9.1 

9.4 

8.8 




Trichloroacetic acid d 

1 


ND 

2.2 

2.0 

2.3 




Bromodichloroacetic acid 

1 


3.1 

8.1 

7.6 

7.8 




Dibromochloroacetic acid 

1 


3.2 

7.6 

7.2 

7.1 




Tribromoacetic acid 

2 


ND 

2.2 

2.0 

2.2 




HAA5 f 



11 

18 

18 

17 




HAA9 9 



23 

43 

42 

44 




DXAA h 



17 

22 

22 

23 




TXAA' 



6.3 

20 

19 

19 




Haloacetonitriles 










Chloroacetonitrile 

0.1 

ND 

ND 

0.2 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

0.2 

ND 

ND 

Dichloroacetonitrile* 3 

0.1 

ND 

0.4 

0.6 

0.6 

0.7 

0.8 

0.2 

0.2 

Bromochloroacetonitrile d 

.L '. - 

ND 

0.6 

1 

1 

1 

1 

2 

2 

Dibromoacetonitrile d 

!,:L 

ND 

0.6 

2 

2 

2 

2 

NR 1 

NR 

T richloroacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 


ND 

ND 




ND 

Dibromochloroacetonitrile 

0.5 

ND 


0.6 

ND 




ND 

T ribromoacetonitrile 

0.5 

ND 


ND 

ND 




ND 

Haloacetaldehydes 










Dichloroacetaldehvde 

0.22 

ND 

0.7 

1 

2 

0.9 

0.9 

0.4 

0.9 

Bromochloroacetaldehvde 


ND 

0.6 

1 

0.8 

0.9 

0.9 

0.3 

0.4 

Chloral hydrate d 

0.1 

ND 

ND 

1 

NR 

0.9 

0.8 

0.2 

0.3 

T ribromoacetaldehvde 

0.1 

ND 

0.2 

0.8 

0.4 

ND 

ND 

ND 

ND 


80 






























































Table 13 (continued) 


09/10/2001 

MRL a 

Plant 11 b 

Compound 

Ud/L 

Raw 

Filt Eff 

Clearwell 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloketones 










Chloropropanone 

0.1 

ND 

0.1 

ND 

0.1 

ND 

0.1 

ND 

ND 

1.1-Dichloropropanone d 

0.10 

ND 

0.4 

0.2 

0.3 

0.2 

0.3 

0.1 

0.1 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

0.1 

ND 

0.4 

0.2 

0.2 

0.2 

0.2 

ND 

ND 

1,1,1 -T richloropropanone d 

0.1 

ND 

0.3 

0.5 

0.5 

0.3 

0.2 

ND 

ND 

1.1.3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

0.1 

ND 

0.2 

0.4 

0.4 

ND 

ND 

ND 

ND 

1,1,1 -T ribromopropanone 

2.5 

ND 

NR 

ND 

ND 

ND 

NR 

ND 

NR 

1,1,3-Tribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1.3.3-Tetrachloroprooanone 


ND 

0.6 

0.3 

0.1 

ND 

ND 

ND 

ND 

1.1.1,3-Tetrachloroprooanone 

0.1Q 

ND 

ND 

0.5 

0.1 

ND 

ND 

ND 

ND 

1,1,3,3-T etrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 










Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.1 Oi 

ND 

ND 

0.2 

0.2 

0.1 

ND 

ND 

ND 

Chloropicrin d 

0 1 

ND 

ND 

ND 

ND 

ND 

0.1 

ND 

ND 

Bromodichloronitromethane 

0.5 

ND 


ND 

ND 




0.6 

Dibromochloronitromethane 

0.5 

ND 


ND 

ND 




0.5 

Bromopicrin 

0.5 

ND 


ND 

ND 




ND 

Miscellaneous Compounds 










Methyl ethyl ketone 

0.5 

0.6 


ND 

ND 

0.6 


0.7 


Methvl tertian/ butvl ether 

0 2 

ND 


ND 

ND 

ND 


ND 


Benzyl chloride 

0.25 

ND 

NR 

ND 

ND 

ND 

NR 

ND 

NR 

1.1,2,2-Tetrabromo-2-chloroethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


81 









































Table 14. DBP results at plant 12 (9/10/01) 


09/10/2001 

MRL a 

H9 /L 

Plant 12 k 

Compound 

Raw 

Pre-Treat 

Filt Inf 

Filt Eff 

Plant Eff 

DS/Ave 

DS/Max 

Halomethanes 









Chloromethane 

0.2 

ND C 


ND 


ND 

ND 


Bromomethane 

0.2 

ND 


ND 


ND 

ND 


Bromochloromethane 

0.5 

ND 


ND 


ND 

ND 


Dibromomethane 

0.5 

ND 


ND 


ND 

ND 


Chloroform d 

0.1 

ND 

0.4 

9 

14 

14 

17 

19 

Bromodichloromethane d 

0.2 

ND 

NR 1 

9 

NR 

13 

15 

NR 

Dibromochloromethane d 

0.25 

ND 

NR 

4 

NR 

6 

7 

NR 

Bromoform d 

0.5 

ND 

ND 

1 

NR 

1 

2 

NR 

THM4 e 


ND 

NR 

23 

NR 

34 

41 

NR 

Dichloroiodomethane 

0.5 

ND 

NR 

6 

NR 

7 

10 

NR 

Bromochloroiodomethane 

0.5 

ND 

ND 

1 

2 

2 

2 

2 

Dibromoiodomethane 

0.52 

ND 

ND 

0.6 

0.8 

1 

1 

ND 

Chlorodiiodomethane 

0.25 

ND 

NR 

0.4 

NR 

0.5 

2 

NR 

Bromodiiodomethane 

0.25 

ND 

ND 

ND 

ND 

0.3 

0.6 

ND 

Iodoform 

0.25 

ND 

NR 

ND 

NR 

ND 

0.3 

NR 

Carbon tetrachloride 

0.2 

ND 


ND 


ND 

ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 









Monochloroacetic acid d 

2 


ND 

2.8 

2.8 

3.0 

2.1 


Monobromoacetic acid d 

1 


ND 

1.0 

1.2 

1.3 

ND 


Dichloroacetic acid d 

1 


ND 

26 

26 

29 

26 


Bromochloroacetic acid d 

1 


ND 

15 

16 

19 

14 


Dibromoacetic acid d 

1 


ND 

4.8 

4.9 

6.7 

5.9 


Trichloroacetic acid d 

1 


ND 

8.0 

9.8 

11 

9.0 


Bromodichloroacetic acid 

1 


ND 

4.9 

5.9 

6.9 

5.6 


Dibromochloroacetic acid 

1 


ND 

1.1 

1.3 

1.8 

1.3 


Tribromoacetic acid 

2 


ND 

ND 

ND 

ND 

ND 


HAA5 f 



ND 

43 

45 

51 

43 


HAA9 9 



ND 

64 

68 

79 

64 


DXAA h 



ND 

46 

47 

55 

46 


TXAA' 



ND 

14 

17 

20 

16 


Haloacetonitriles 









Chloroacetonitrile 

0.1 

ND 

ND 

ND 

0.1 

0.1 

0.1 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

0.2 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.1 

ND 

ND 

1 

2 

3 

2 

3 

Bromochloroacetonitrile d 

0.1 

ND 

ND 

0.6 

0.9 

1 

1 

1 

Dibromoacetonitrile d 

0.1 

ND 

ND 

0.2 

0.4 

0.6 

0.9 

1 

T richloroacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 


ND 


ND 



Dibromochloroacetonitrile 

0.5 

ND 


ND 


ND 



Tribromoacetonitrile 

0.5 

ND 


ND 


ND 



Haloacetaldehydes 









Dichloroacetaldehyde 

0.22 

1 

0.7 

3 

5 

4 

6 

6 

Bromochloroacetaldehyde 

0.5 

ND 

ND 

1 

2 

2 

1 

1 

Chloral hydrate d 

0.1 

0.5 

ND 

2 

2 

2 

2 

2 

T ribromoacetaldehyde 

0.1 

0.7 

0.1 

0.7 

0.9 

0.3 

0.1 

ND 


82 




























































Table 14 (continued) 


09/10/2001 

MRL a 

H9 /l 

Plant 12 k 

Compound 

Raw 

Pre-T reat 

Filt Inf 

Filt Eff 

Plant Eff 

DS/Ave 

DS/Max 

Haloketones 









Chloropropanone 

0.1 

ND 

ND 

0.1 

0.1 

0.1 

0.2 

0.3 

1,1-Dichloropropanone d 

0.10 

ND 

0.1 

0.8 

1 

1 

0.8 

0.9 

1,3-Dichloropropanone 

0.1 

ND 

ND 

0.2 

ND 

ND 

ND 

ND 

1.1-Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T richloropropanone d 

0.1 

ND 

ND 

0.1 

0.3 

0.4 

ND 

ND 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1.3.3-Tetrachloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1.1.3-Tetrachloropropanone 

0.10 

ND 

0.2 

0.5 

0.5 

0.5 

0.4 

0.3 

1,1,3,3-Tetrabromopropanone 

2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 









Bromonitromethane 

0.1 

ND 

ND 

ND 

0.4 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

0.2 

ND 

ND 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin d 

0.1 

ND 

ND 

0.4 

0.6 

0.9 

1 

2 

Bromodichloronitromethane 

0.5 

ND 


1 


2 



Dibromochloronitromethane 

0.5 

ND 


2 


2 



Bromopicrin 

0.5 

ND 


2 


ND 



Miscellaneous Compounds 









Methyl ethyl ketone 

0.5 

ND 


0.6 


ND 

0.6 


Methyl tertiarv butyl ether 

0.2 

ND 


ND 


ND 

ND 


Benzyl chloride 

0.25 

ND 

NR 

ND 

NR 

ND 

ND 

NR 

1,1,2,2-Tetrabromo-2-chloroethane 

0.5 

ND 

NR 

ND 

NR 

ND 

ND 

NR 


83 








































Table 15. Additional target DBP results (pg/L) at plant 11 (9/10/01) 


9/10/01 

Plant 1 l a 

Compound 

Raw 

FI 

CWI 

CWE 

PE 

DS 

SDS 

Monochloroacetaldehyde 

0 

0 

0.2 

0 

0 

0 

0 

Dichloroacetaldehyde 

0 

0 

1.4 

1.2 

3.2 

2.8 

3.5 

Bromochloroacetaldehyde 

0 

0 

1.0 

1.5 

2.8 

2.6 

1.8 

3,3-Dichloropropenoic acid 

0 

0 

0.8 

0.9 

0.7 

0.6 

0.6 

Bromochloromethylacetate 

0 

0 

0 

0 

0 

0 

0 

2,2- Dichloroacetamide 

0 

0 

0 

2.5 

2.8 

2.7 

2.4 

TOX (pg/L as C1‘) 

33.5 

48.1 

299 

129 

126 

118 

121 

Cyanoformaldehyde 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

5-Keto-l-hexanal 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

6 - Hydroxy- 2 - hexanone 

<0.1 

0.8 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

Dimethylglyoxal 

<0.1 

<0.1 

1.1 

1.5 

1.2 

0.8 

1.5 

trans- 2-Hexenal 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 


*Plant 11 sampled at (1) raw water, (2) filter influent (FI), (3) clearwell influent (CWI), (4) 
clearwell effluent (CWE), (5) finished water at plant effluent (PE), (6) distribution system (DS) 
at average detention time, and (6) SDS at maximum detection time. 


Table 16. Additional target DBP results (pg/L) at plant 12 (9/10/01) 


9/10/01 

Plant 12 b 

Compound 

Raw 

PT 

FI 

FE 

PE 

DS 

SDS 

Monochloroacetaldehyde 

0 

0.3 



1.2 


1.8 

Dichloroacetaldehyd e 

0 

0.4 

4.2 

6.2 

5.8 

6.5 

6.8 

Bromochloroacetaldehyde 

0 

2.1 

2.4 

3.1 

3.0 

2.5 

2.1 

3,3-Dichloropropenoic acid 

0 

0 

0.5 

0 

0 

0 

0 

Bromochloromethylacetate 

0 

0 

0 

0 

0 

0 

0 

2 ,2-Dichloroacetamide 

0 

0 

4.5 

4.4 

5.6 

5.1 

5.5 

TOX (pg/L as Cl') 

6.6 

35.0 

196 

223 

260 

245 

165 

Cyanoformaldehyde 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

5-Keto-l-hexanal 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

6 - Hydroxy- 2 - hexanone 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

Dimethylglyoxal 

<0.1 

<0.1 

2.4 

3.1 

2.5 

2.0 

2.9 

Turns'-2-Hexenal 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 


b Plant 12 sampled at (1) raw water, (2) pre-treated water (PT), (3) filter influent (FI), (4) filter 
effluent (FE), (5) finished water at plant effluent (PE), (6) distribution system (DS) at average 
detention time, and (7) SDS at maximum detection time. 


84 
















































Table 17. Halogenated furanone results (|ag/L) at plant 11 (9/10/01) 


Compound 

FI 

FE 

CWE 

PE 

DS/ave 

SDS/max 

BMX-1 

< 0.02 

0.05 

0.12 

0.17 

0.14 

0.21 

BEMX-1 

0.02 

< 0.02 

< 0.02 

( 0 . 01 ) 

< 0.02 

< 0.02 

( 0 . 01 ) 

< 0.02 

BMX-2 

< 0.02 

< 0.02 

( 0 . 011 ) 

< 0.02 

( 0 . 011 ) 

< 0.02 

( 0 . 016 ) 

< 0.02 

( 0 . 015 ) 

< 0.02 

( 0 . 013 ) 

BEMX-2 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

BMX-3 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

BEMX-3 

< 0.02 

0.37 

0.31 

0.20 

< 0.02 

0.49 

MX 

< 0.02 

< 0.02 

0.02 

0.02 

0.85 

NA 

EMX 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

NA 

ZMX 

< 0.02 

< 0.02 

0.09 

< 0.02 

< 0.02 

NA 

Mucochloric acid (ring) 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

NA 

Mucochloric acid (open) 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

NA 


Table 18. Halogenated furanone results (pg/L) at plant 12 (9/10/01) 


Compound 

Raw 

PT 

FI 

FE 

PE 

DS/ave 

SDS/max 

BMX-1 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

0.09 

0.08 

0.03 

BEMX-1 

0.03 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

BMX-2 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

0.03 

0.02 

< 0.02 

( 0 . 017 ) 

BEMX-2 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

BMX-3 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

BEMX-3 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

0.04 

< 0.02 

MX 

< 0.02 

< 0.02 

< 0.02 

0.08 

< 0.02 

( 0 . 014 ) 

NA 

NA 

EMX 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

NA 

NA 

ZMX 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

NA 

NA 

Mucochloric acid (ring) 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

NA 

NA 

Mucochloric acid (open) 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

< 0.02 

NA 

NA 


85 







































Table 19. DBP results at plant 11 (11/5/01) 


11/05/2001 

MRL a 

Plant 11 m 

Compound 

L 

Raw 

Filt Inf 

Clearwell 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Halomethanes 










Chloromethane 

0.2 

ND C 


ND 

ND 

ND 


ND 


Bromomethane 

0.2 

ND 


ND 

ND 

ND 


ND 


Bromochtoromethane 

0.5 

ND 


ND 

ND 

ND 


ND 


Dibromomethane 

0.5 

ND 


NQ 

ND 

ND 


ND 


Chloroform d 

0.5 

ND 

ND 

ND 

5 

7 

8 

8 

9 

Bromodichloromethane d 

0.1 

ND 

0.1 

0.4 

14 

17 

17 

18 

20 

Dibromochloromethane d 

0.1 

ND 

ND 

0.3 

15 

16 

18 

18 

19 

Bromoform d 

0.11 

ND 

ND 

ND 

3 

3 

4 

3 

3 

THM4 e 


ND 

0.1 

0.7 

37 

43 

47 

47 

51 

Dichloroiodomethane 

0.5 

ND 

ND 

ND 

1 

2 

NR 1 

2 

NR 

Bromochloroiodomethane 

0.25 

ND 


ND 

0.4 

0.3 


0.4 


Dibromoiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.5 

ND 

NR 

ND 

ND 

ND 

NR 

ND 

NR 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 

ND 


ND 

ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 










Monochloroacetic acid d 

2 


ND 

ND 

ND 

ND 


ND 


Monobromoacetic acid d 

L 


ND 

ND 

1.1 

1.1 


1.1 


Dichloroacetic acid d 

1 


ND 

ND 

8.8 

11 


11 


Bromochloroacetic acid d 

1 


ND 

ND 

10 

11 


11 


Dibromoacetic acid d 

1 


ND 

ND 

7.9 

8.0 


8.0 


Trichloroacetic acid' 1 

1 


ND 

ND 

4.7 

5.3 


4.5 


Bromodichloroacetic acid 

1 


ND 

ND 

9.6 

11 

% 

10 


Dibromochloroacetic acid 

1 


ND 

ND 

6.2 

6.9 


5.9 


Tribromoacetic acid 

2 


ND 

ND 

ND 

ND 


ND 


HAA5 f 



ND 

ND 

23 

25 


25 


HAA9 9 



ND 

ND 

48 

54 


52 


DXAA h 



ND 

ND 

27 

30 


30 


TXAA' 



ND 

ND 

21 

23 


?fl 


Haloacetonitriles 










Chloroacetonitrile 

0,1 

ND 

ND 

ND 

ND 

0.3 

ND 

0.4 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.10 

ND 

ND 

ND 

1 

1 

2 

2 

2 

Bromochloroacetonitrile d 

0.1 

ND 

ND 

ND 

NR 

NR 

2 

2 

2 

Dibromoacetonitrile d 

0.14 

ND 

ND 

ND 

2 

2 

1 

2 

2 

T richloroacetonitrile d 

0,1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 


ND 

ND 




ND 

Dibromochloroacetonitrile 

0.5 

ND 


ND 

0.6 




0.5 

Tribromoacetonitrile 

0.90 

ND 


ND 

ND 




ND 

Haloacetaldehydes 










Dichloroacetaldehvde 

1.1 

ND 

NP 

ND 

1 

2 

3 

3 

3 

Bromochloroacetaldehvde 

0.5 

ND 

ND 

ND 

1 

1 

1 

1 

1 

Chloral hvdrate d 

0.1 

ND 

ND 

0.1 

1 

1 

1 

2 

2 

T ribromoacetaldehyde 

0.5 

ND 

ND 

ND 

<0.5 n 

ND 

ND 

ND 

ND 


86 



































































Table 19 (continued) 


11/05/2001 

MRL a 

Plant 11 m 

Compound 


Raw 

Filt Inf 

Clearwell 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloketones 










Chloropropanone 

0.1 

ND 

ND 

ND 

0.2 

0.1 

0.3 

ND 

ND 

1.1-Dichloroorooanone d 


ND 

0.2 

0.1 

0.5 

0.6 

0.7 

0.8 

0.8 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1-Trichloropropanone d 

0.1 

ND 

ND 

ND 

0.8 

0.7 

0.7 

0.5 

0.4 

1.1,3-T richloroprooanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

1.0 

ND 

NR 

ND 

ND 

ND 

NR 

ND 

ND 

1,1,1 -T ribromopropanone 

0.29 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

1.1,3-Tribromopropanone 

0.14 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1,3.3-Tetrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-T etrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 










Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

ND 

ND 

ND 

0.2 

0.3 

0.3 

0.4 

0.4 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin d 

.. U 1 

ND 

ND 

ND 

0.1 

0.2 

0.5 

1 

1 

Bromodichloronitromethane 

0.5 

ND 


ND 

0.7 




1 

Dibromochloronitromethane 

2 

ND 


ND 

ND 




ND 

Bromopicrin 

2 

ND 


ND 

ND 




ND 

Miscellaneous Compounds 










Methyl ethyl ketone 

0.5 

2 


ND 

0.8 

0.7 


0.9 


Methvl tertiary butvl ether 

o : 

ND 


ND 

ND 

ND 


ND 


Benzvl chloride 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1,2.2-Tetrabromo-2-chloroethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


m Plant 11 sampled at (1) raw water, (2) filter influent, (3) clearwell influent, (4) plant effluent, 
DS at (5) average and (6) maximum detention times, and 
SDS testing of plant effluent at (7) average and (8) maximum detention times 
n <0.5: Concentration less than MRL (i.e., 0.5 pg/L) 


87 









































Table 20. DBP results at plant 12 (11/15/01) 


11/15/2001 

MRL a 

Plant 12 k 

Compound 

mq/l 

Raw 

Pre-Treat 

Filt Inf 

Filt Eff 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Halomethanes 











Chloromethane 

0.2 

NP C 


ND 


ND 

ND 


ND 


Bromomethane 

0.2 

ND 


ND 


ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 


ND 


ND 

ND 


ND 


Dibromomethane 

0.5 

ND 


ND 


ND 

ND 


ND 


Chloroform 11 

0.1 

ND 

0.3 

7 

5 

5 

11 

13 

11 

11 

Bromodichloromethane d 

0.1 

ND 

0.3 

11 

8 

10 

21 

25 

20 

19 

Dibromochloromethane d 

0.1 

ND 

ND 

6 

5 

6 

15 

18 

14 

14 

Bromoform d 

0.11 

ND 

ND 

2 

1 

2 

9 

9 

7 

8 

THM4 e 


ND 

0.6 

26 

19 

23 

56 

65 

52 

52 

Dichloroiodomethane 

0.5 

ND 

NR 1 

11 

NR 

11 

15 

NR 

14 

NR 

Bromochloroiodomethane 

0.25 

ND 


3 

2 

3 

5 

4 

4 

3 

Dibromoiodomethane 

0.52 

ND 

ND 

1 

NR 

2 

3 

3 

3 

NR 

Chlorodiiodomethane 

0.5 

ND 

NR 

0.6 

NR 

2 

1 

NR 

1 

NR 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

0.7 

0.7 

0.7 

ND 

ND 

Iodoform 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 

ND 


ND 


ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 











Monochloroacetic acid d 

2 


ND 

3.7 

3.3 

5.5 

2.1 


2.8 


Monobromoacetic acid d 

1 


ND 

ND 

ND 

ND 

1.0 


2.7 


Dichloroacetic acid d 

1 


1.1 

19 

18 

22 

17 


27 


Bromochloroacetic acid d 

1 


ND 

21 

21 

18 

18 


21 


Dibromoacetic acid d 

1 


ND 

8.6 

8.6 

11 

8.2 


15 


Trichloroacetic acid d 

1 


ND 

4.5 

4.2 

5.7 

7.2 


7.1 


Bromodichloroacetic acid 

1 


ND 

3.8 

3.9 

5.7 

5.4 


6.7 


Dibromochloroacetic acid 

1 


ND 

1.8 

1.7 

2.8 

2.2 


2.8 


Tribromoacetic acid 

2 


ND 

ND 

ND 

ND 

ND 


ND 


HAA5 f 



1.1 

36 

34 

44 

36 


55 


HAA9 9 



1,1 

62 

61 

71 

61 


85 


DXAA h 



1.1 

49 

48 

51 

43 


63 


TXAA' 



ND 

10 

10 

14 

15 


17 


Haloacetonitriles 











Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

0.4 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.10 

ND 

ND 

1 

0.7 

2 

2 

2 

2 

2 

Bromochloroacetonitrile d 

0.1 

ND 

ND 

0.7 

0.4 

1 

3 

2 

3 

2 

Dibromoacetonitrile d 

0.14 

ND 

ND 

0.5 

0.2 

0.9 

2 

0.9 

2 

1 

Trichloroacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 


ND 


ND 




ND 

Dibromochloroacetonitrile 

0.5 

ND 


ND 


ND 




ND 

T ribromoacetonitrile 

0.90 

ND 


ND 


ND 




ND 

Haloacetaldehydes 











Dichloroacetaldehvde 

0.22 

£4Q 

ND 

3 

2 

3 

4 

4 

5 

5 

Bromochloroacetaldehvde 

0.5 

ND 

ND 

1 

0.5 

2 

4 

4 

3 

4 

Chloral hydrate d 

0.1 

ND 

0.2 

1 

1 

1 

2 

2 

1 

2 

T ribromoacetaldehyde 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


88 
































































Table 20 (continued) 


11/15/2001 

MRL* 

mq/l 

Plant 12 k 

Compound 

Raw 

Pre-Treat 

Filt Inf 

Filt Eff 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloketones 











Chloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

0.6 

ND 

1,1-Dichloropropanone d 

0.10 

ND 

0.2 

0.7 

0.8 

0.8 

0.8 

0.8 

0.9 

0.7 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

0.1 

0.1 

ND 

ND 

1,1,1-Trichloropropanone d 

0.1 

ND 

ND 

0.2 

ND 

0.3 

0.4 

0.3 

0.1 

0.1 

1,1,3-Trichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T ribromopropanone 

2.5 

ND 

NR 

ND 

NR 

ND 

ND 

NR 

ND 

NR 

1.1.3-Tribromopropanone 

0.14 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1.3.3-Tetrachloroprooanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1.1,3-Tetrachlorocronanone 

0.10 

ND 

ND 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 











Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

ND 

ND 

0.3 

0.3 

0.4 

0.6 

0.9 

ND 

0.4 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin d 

0.1 

ND 

ND 

0.3 

0.2 

0.7 

1 

0.9 

2 

1 

Bromodichloronitromethane 

0.5 

ND 


1 


1 




ND 

Dibromochloronitromethane 

0.5 

ND 


2 


1 




1 

Bromopicrin 

0.5 

ND 


2 


2 




0.7 

Miscellaneous Compounds 











Methvl ethvl ketone 

0,5 

1 


ND 


0.7 

0.8 


1 


Methyl tertiary butyl ether 

0.2 

ND 


ND 


ND 

ND 


0.3 


Benzyl chloride 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

1,1,2,2-T etrabromo-2-chloroethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


89 










































Table 21. Occurrence of other DBPs a at plant 12: 


a DBPs detected by broadscreen gas chromatography/mass spectrometry (GC/MS) technique. 
b Compounds listed in italics were confirmed through the analysis of authentic standards; haloacids and 
non-halogenated carboxylic acids identified as their methyl esters. 
c Exact isomer not known 


Halomethanes 

Bromodichloromethane 3 

Dibromochloromethane 

Bromoform 

Dichloroiodomethane 

Bromochloroiodomethane 

Dibromoiodomethane 

Chlorodiiodomethane 

Bromodiiodomethane 

Haloacids 
Iodoacetic acid 
Dichloroacetic acid 
Bromochloroacetic acid 
Dibromoacetic acid 
Iodobromoacetic acid 
Tribromoacetic acid 

3.3- Dichloropropenoic acid 

3.3- Dibromopropenoic acid 
Iodobromopropenoic acid 0 (2 isomers) 
cis-2-Bromo-butenedioic acid 
2-Iodo-3-methylbutenedioic acid 

Haloacetonitriles 

Bromochloroacetonitrile 

Dibromoacetonitrile 

Haloaldehydes 

2-Bromo-2-methylpropanal 


plant effluent (11/15/01) _ 

Haloketones 

1,1 -Dibromo-3,3-dichloropropanone 

1.3- Dibromo-l, 3-dichloropropanone 

1.1.3- Tribromo-3-chloropropanone 

1.1.3.3- Tetrabromopropanone 
Pentachloropropanone 

Miscellaneous Halogenated DBPs 

Dibromoaniline 

Dibromodichloroaniline 

Tribromochloroaniline 

Non-halogenated DBPs 

Acetone 
Glyoxal 
Hexanoic acid 
Heptanoic acid 
Octanoic acid 
Nonanoic acid 
Decanoic acid 
Dodecanoic acid 
Tetradecanoic acid 
Hexanedioic acid 
Decanedioic acid 
Undecanedioic acid 


90 
















Table 22. DBP results at plant 11 (2/11/02) 


02 / 11/2002 

MRL a 

uq/L 

Plant 11 m 

Compound 

Raw 

Filt Inf 

Clearwell 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Halomethanes 










Chloromethane 

0.2 

o ! 

Q 

Z 


ND 

ND 

ND 


ND 


Bromomethane 

0.2 

ND 


ND 

ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 


ND 

ND 

ND 


ND 


Dibromomethane 

0,5 

ND 


ND 

ND 

ND 


ND 


Chloroform d 

0.2 

ND 

NR 1 

4 

5 

7 

NR 

6 

NR 

Bromodichloromethane d 

0.5 

ND 

NR 

4 

9 

10 

NR 

11 

NR 

Dibromochloromethane d 

0.25 

ND 

NR 

5 

10 

11 

NR 

12 

NR 

Bromoform d 

0-5 

ND 

NR 

2 

4 

4 

NR 

4 

NR 

THM4 e 


ND 

NR 

15 

28 

32 

NR 

33 

NR 

Dichloroiodomethane 

1.0 

ND 

NR 

<1° 

<1 

<1 

NR 

<1 

NR 

Bromochloroiodomethane 

0.5 

ND 

ND 

<0.5" 

<0.5 

<0.5 

ND 

0.7 

ND 

Dibromoiodomethane 

0,53 

ND 

ND 

ND 

ND 

0.6 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

2.2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 

ND 


ND 

ND 

ND 


ND 


Tribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 










Monochloroacetic acid d 

2 


ND 

3.0 

2.8 

2.8 


3.2 


Monobromoacetic acid d 

1 


ND 

1.0 

1.4 

1.5 


1.6 


Dichloroacetic acid d 

1 


4.8 

6.6 

6.7 

9.2 


8.0 


Bromochloroacetic acid d 

1 


ND 

5.0 

6.3 

6.3 


6.2 


Dibromoacetic acid d 

1 


ND 

5.7 

6.1 

5.5 


5.3 


Trichloroacetic acicf 1 

1 


2.0 

3.4 

4.4 

4.7 


4.0 


Bromodichloroacetic acid 

1 


ND 

6.6 

9.0 

8.8 


8.6 


Dibromochloroacetic acid 

1 


ND 

6.2 

9.1 

8.7 


8.5 


Tribromoacetic acid 

2 


ND 

ND 

ND 

4.6 


ND 


HAA5 f 



6.8 

20 

21 

24 


22 


HAA9 9 



6.8 

38 

46 

52 


45 


DXAA h 



4.8 

17 

19 

21 


20 


TXAA' 



2.0 

16 

23 

27 


21 


Haloacetonitriles 










Chloroacetonitrile 

0,1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

2.5 

ND 

NR 

<1 

<1 

<1 

NR 

<1 

NR 

Bromochloroacetonitrile d 

0.5 

ND 

ND 

0.5 

2 

2 

NR 

2 

NR 

Dibromoacetonitrile d 

1.0 

ND 

ND 

<1 

2 

2 

NR 

2 

NR 

T richloroacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 


ND 

ND 




ND 

Dibromochloroacetonitrile 

0.5 

ND 


ND 

ND 




ND 

T ribromoacetonitrile 

0.90 

ND 


ND 

ND 




ND 

Haloacetaldehydes 










Dichloroacetaldehvde 

0.98 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloroacetaldehvde 

0.5 

ND 

ND 

ND 

06 

0.7 

0.7 

0.8 

0.8 

Chloral hvdrate d 

0.1 

0,5 

0.2 

0.2 

Q,3 

0.3 

0.3 

0.5 

0*4 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


91 





























































Table 22 (continued) 


02/11/2002 

MRL a 

Plant 11 m 

Compound 

r ' 

Raw 

Filt Inf 

Clearwell 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Haloketones 










ChloroDropanone 

0.1 

ND 

0.1 

1 

1 

1 

0.5 

1 

1 

1,1-Dichloropropanone d 

1.0 

ND 

1 

1 

<1 

<1 

<1 

<1 

<1 

1,3-Dichloropropanone 

0.1 

0.2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

0.1 

ND 

ND 

0.4 

0.3 

0.4 

0.2 

0.2 

0.2 

1,1.1 -T richloropropanone d 

0.5 

ND 

<0.5 

0.9 

0.8 

0.8 

0.9 

0.7 

0.9 

1.1.3-T richloroDroDanone 


ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1.1-dichloroDroDanone 

0.1 

ND 

ND 

0.2 

0.4 

ND 

ND 

0.1 

ND 

1,1,1-Tribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-Tribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1,3.3-Tetrachlorooropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1.1,3-Tetrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 










Chloronitromethane 

NA 

ND 


ND 

ND 

ND 


ND 


Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

0.1 

ND 

ND 

ND 

Dichloronitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloronitromethane 

i : 

ND 

ND 

0.1 

0.1 

0.1 

0.2 

0.2 

0.2 

Dibromonitromethane 

0. j. 

ND 

ND 

ND 

ND 

0.1 

ND 

0.1 

ND 

Chlorooicrin d 

o 

ND 

ND 

0.3 

0.4 

0.2 

0.4 

0.4 

0.7 

Bromodichloronitromethane 

2 

ND 


ND 

ND 




ND 

Dibromochloronitromethane 

2 

ND 


ND 

ND 




ND 

Bromopicrin 

0.5 

ND 


ND 

1 




ND 

Miscellaneous Compounds 










Methyl ethyl ketone 

0.5 

ND 


ND 

ND 

ND 


ND 


Methvl tertiarv butvl ether 

0.2 

ND 


ND 

ND 

ND 


ND 


Benzvl chloride 

^J... 

ND 

NR 

ND 

ND 

ND 

NR 

ND 

NR 

1,1,2,2-Tetrabromo-2-chloroethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


°<1.0: Concentration less than MRL (e.g., 1.0 pg/L) 


92 










































Table 23. DBP results at plant 12 (2/12/02) 


02 / 12/2002 

MRL d 

Plant 12* 

Compound 

IJd/L 

Raw 

Pre-T reat 

Filt Inf 

Filt Eff 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Halomethanes 











Chloromethane 

0,2 


ND C 

ND 


ND 

ND 


ND 


Bromomethane 

0.2 


ND 

ND 


ND 

ND 


ND 


Bromochloromethane 

0.5 


ND 

ND 


ND 

ND 


ND 


Dibromomethane 

0.5 


ND 

ND 


ND 

ND 


ND 


Chloroform* 

n 

'..0 

0.4 

3 

NR 1 

3 

3 

NR 

3 

NR 

Bromodichloromethane d 

0.5 

ND 

0.8 

12 

NR 

14 

15 

NR 

12 

NR 

Dibromochloromethane d 

0.25 

ND 

1 

19 

NR 

21 

23 

NR 

19 

NR 

Bromoform d 

0.5 

ND 

0.5 

17 

NR 

19 

19 

NR 

16 

NR 

THM4 e 


NP 

3 

51 

NR 

57 

60 

NR 

50 

NR 

Dichloroiodomethane 

1.0 

ND 

NR 

<1° 

NR 

<1 

<1 

NR 

<1 

NR 

Bromochloroiodomethane 

0.5 

ND 

ND 

2 

NR 

2 

3 

NR 

2 

NR 

Dibromoiodomethane 

0.53 

ND 

ND 

3 

NR 

4 

4 

NR 

3 

NR 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.52 

ND 

ND 

ND 

ND 

<0.5 n 

<0.5 

<0.5 

ND 

ND 

Iodoform 

2.2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

o 


ND 

ND 


ND 

ND 


ND 


Tribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 











Monochloroacetic acid d 

2 


3.9 

3.2 

3.2 

3.0 

2.1 


2.6 


Monobromoacetic acid d 

1 


1.3 

2.2 

2.2 

2.1 

2.5 


2.0 


Dichloroacetic acid d 

1 


7.8 

11 

11 

10 

18 


9.6 


Bromochloroacetic acid d 

1 


6.9 

14 

13 

14 

22 


14 


Dibromoacetic acid d 

1 


6.6 

16 

14 

18 

22 


16 


Trichloroacetic acid d 

1 


ND 

2.4 

2.2 

3.1 

3.8 


2.7 


Bromodichloroacetic acid 

1 


4.7 

6.5 

8.0 

9.0 

9.7 


9.1 


Dibromochloroacetic acid 

1 


1.2 

6.3 

5.9 

8.1 

8.8 


7.5 


Tribromoacetic acid 

2 


ND 

ND 

ND 

ND 

ND 


ND 


HAA5 f 



20 

35 

33 

36 

48 


33 


HAA9 9 



32 

62 

60 

67 

89 


64 


DXAA h 



21 

41 

38 

42 

62 


40 


TXAA' 



5.9 

15 

16 

20 

22 


19 


Haloacetonitriles 











Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

2,5 

NP 

ND 

<1 

NR 

<1 

<1 

NR 

<1 

<1 

Bromochloroacetonitrile d 

0.5 

ND 

NR 

1 

NR 

2 

2 

NR 

2 

NR 

Dibromoacetonitrile d 

1,0 

ND 

NR 

1 

NR 

2 

2 

NR 

2 

NR 

T richloroacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 


ND 

ND 


ND 




ND 

Dibromochloroacetonitrile 

0.5 


ND 

ND 


ND 




ND 

T ribromoacetonitrile 

0.90 


ND 

ND 


ND 




ND 

Haloacetaldehydes 











Dichloroacetaldehvde 

0.98 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloroacetaldehvde 

0.5 

ND 

ND 

2 

2 

2 

2 

2 

2 

2 

Chloral hydrate d 

0.1 

0.0 

ND 

0.7 

0-5 

0.7 

0.9 

1 

0.8 

0.7 

Tribromoacetaldehyde 

0.1 

ND 

ND 

2 

1 

2 

1 

0.6 

2 

2 


93 































































Table 23 (continued) 


02/12/2002 

MRL a 

Plant 12 k 

Compound 

hr /l 

Raw 

Pre-Treat 

Filt Inf 

Filt Eff 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloketones 











Chloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 t 1-Dichloropropanone d 

1.0 

ND 

<1 

<1 

<1 

<1 

<1 

<1 

<1 

<1 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

0.1 

ND 

0.3 

0.4 

0.3 

0.4 

0.2 

0.2 

0.4 

0.4 

1,1.1 -T richloropropanone d 

0.5 

ND 

<0.5 

0.6 

<0.5 

0.6 

<0.5 

<0.5 

0.6 

0.6 

1.1.3-Trichloroprooanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1.1 -dichloropropanone 

0.1 

ND 

ND 

0.5 

0.1 

0.5 

0.1 

ND 

0.6 

0.2 

1.1.1 -T ribromopropanone 

0 1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-Tribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1.1,3,3-Tetrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-Tetrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 











Chloronitromethane 

MA 


ND 

ND 


ND 

ND 


ND 


Bromonitromethane 

0.1 

ND 

ND 

ND 

0.1 

0.2 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.10 

ND 

ND 

0.3 

0.2 

0.3 

0.3 

0.3 

0.2 

0.2 

Bromochloronitromethane 

0.1 

ND 

0.2 

0.7 

0.7 

0.7 

0.9 

0.9 

0.8 

0.8 

Dibromonitromethane 

0.10 

ND 

ND 

0.5 

0.4 

0.5 

0.4 

0.4 

0.5 

0.6 

Chloropicrin d 

; / 

ND 

ND 

0.4 

0.4 

0.4 

0.7 

1 

0.4 

0.4 

Bromodichloronitromethane 

2 


ND 

ND 


ND 




ND 

Dibromochloronitromethane 

2 


ND 

3 


3 




3 

Bromopicrin 

0.5 


ND 

4 


5 




5 

Miscellaneous Compounds 











Methvl ethvl ketone 

0.5 


ND 

ND 


ND 

ND 


ND 


Methyl tertiary butyl ether 

0.2 


ND 

ND 


ND 

ND 


ND 


Benzyl chloride 

1.0 

ND 

NR 

ND 

NR 

ND 

ND 

NR 

ND 

NR 

1,1,2,2-Tetrabromo-2-chloroethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


94 











































Table 24. Additional target DBP results (pg/L) at plant 11 (2/11/02) 


2/11/02 

Plant ll c 

Compound 

FI 

PE 

DS 

Monochloroacetaldehyde 

0 

0.2 

1.6 

Dichloroacetaldehyde 

0 

1.8 

6.7 

Bromochloroacetaldehyde 

0 

2.0 

3.1 

3,3-Dichloropropenoic acid 

0 

0 

0 

Bromochloromethylacetate 

0 

0 

0 

Monochloroacetamide 

0 

0.4 

0.6 

Monobromoacetamid e 

0 

0.8 

1.0 

2,2-Dichloroacetamide 

0 

1.4 

1.0 

Dibromoacetamide 

0 

1.8 

1.5 

T richloroacetamide 

0 

1.1 

0.8 

TOX (pg/L as CT) 

57.0 

151 

139 

TOBr (pg/L as Br) 

59.3 

79.0 

83.0 

TOC1 (pg/L as CF) 

14.6 

105 

102 

Cyanoformaldehyde 

<0.1 

<0.1 

<0.1 

5-Keto-l-hexanal 

<0.1 

<0.1 

<0.1 

6-Hydroxy-2-hexanone 

<0.1 

<0.1 

<0.1 

Dimethylglyoxal 

<0.1 

1.4 

1.1 

trans-2-Hexenal 

<0.1 

<0.1 

<0.1 


c Plant 11 sampled at (1) FI, (2) PE, and (3) DS at maximum detention time. 


Table 25. Additional target DBP results (pg/L) at plant 12 (2/12/02) 


2/12/02 

Plant 12 d 

Compound 

FI 

FE 

PE 

DS 

Monochloroacetaldehyde 

0.5 

0.5 

0.1 

0.4 

Dichloroacetaldehyde 

2.1 

2.1 

1.3 

2.4 

Bromochloroacetaldehyde 

2.1 

2.1 

4.0 

4.0 

3,3-Dichloropropenoic acid 

0 


0 

0 

Bromochloromethylacetate 

0 


0 

0 

Monochloroacetamide 

1.0 


0.5 

0.8 

Monobromoacetamide 

1.5 


1.1 

1.0 

2,2-Dichloroacetamide 

2.4 


2.0 

1.5 

Dibromoacetamide 

2.5 


2.8 

2.2 

Trichloroacetamide 

0.9 


1.0 

1.1 

TOX (pg/L as CT) 

236 


211 

212 

TOBr (pg/L as Br ) 

250 


229 

212 

TOC1 (pg/L as CT) 

108 


145 

139 

Cyanoformaldehyde 

<0.1 


<0.1 

<0.1 

5-Keto-l-hexanal 

<0.1 


<0.1 

<0.1 

6-Hydroxy-2-hexanone 

<0.1 


<0.1 

<0.1 

Dimethylglyoxal 

3.2 


1.5 

1.9 

trans- 2-Hexenal 

<0.1 


<0.1 

<0.1 


d Plant 12 sampled at (1) FI, (2) FE, (3) PE, and (4) DS at maximum detention time. 


95 



















































Table 26. Halogenated furanone results (pg/L) at plant 11 (2/11/02) 


Compound 

FI 

PE 

D S/max 

BMX-1 

<0.02 

0.08 

<0.02 

BEMX-1 

<0.02 

<0.02 

<0.02 

BMX-2 

<0.02 

<0.02 

<0.02 

BEMX-2 

<0.02 

<0.02 

<0.02 

BMX-3 

<0.02 

<0.02 

<0.02 

BEMX-3 

<0.02 

<0.02 

<0.02 

MX 

<0.02 

<0.02 

0.03 

EMX 

<0.02 

<0.02 

<0.02 

ZMX 

<0.02 

<0.02 

<0.02 

Ox-MX 

<0.02 

<0.02 

<0.02 

Mucochloric acid {ring) 

0.02 

0.04 

0.06 

Mucochloric acid {open) 

<0.02 (0.01) 

0.02 

0.02 


Table 21 . Halogenated furanone results (pg/L) at plant 12 (2/12/02) 


Compound 

FI 

PE 

D S/max 

BMX-1 

< 0.02 

0.06 

< 0.02 

BEMX-1 

< 0.02 

< 0.02 

< 0.02 

BMX-2 

< 0.02 

< 0.02 

< 0.02 

BEMX-2 

< 0.02 

< 0.02 

< 0.02 

BMX-3 

< 0.02 

< 0.02 

< 0.02 

BEMX-3 

< 0.02 

< 0.02 

< 0.02 

MX 

< 0 . 02 ( 0 . 01 ) 

0.03 

< 0.02 ( 0 . 01 ) 

EMX 

< 0.02 

< 0.02 

< 0.02 

ZMX 

< 0.02 

< 0.02 

< 0.02 

Ox-MX 

< 0.02 

< 0.02 

< 0.02 

Mucochloric acid (ring) 

0.13 

0.08 

0.06 

Mucochloric acid (open) 

< 0.02 

< 0.02 

< 0.02 


96 



































Figure 6. March 26, 2001 


Effect of Bromide and Iodide and Disinfection Scheme on 
THM Speciation in Plant Effluents at Plant 11 (Chlorine Dioxide/ 
Chlorine/Chloramines) and Plant 12 (Chloramines Only) 



Halomethanes. Chlorine dioxide/chlorine/chloramine disinfection at plant 11 resulted in 
the formation of 28-49 pg/L of the four regulated trihalomethanes (THM4) in the plant effluent 
in March 2001, September 2001, November 2001, and February 2002. Chloramine disinfection 
at plant 12 resulted in the formation of 23-57 pg/L of THM4 in the plant effluent in March 2001, 
September 2001, November 2001, and February 2002. Even with chloramines only, a fair 
amount of THMs was formed at plant 12. Because of the relatively high amount of TOC and/or 
bromide in these EPA Region 6 waters, THM formation potentials were probably high; thus, 
alternative disinfectants were used to minimize THM formation. 

In March 2001, because of the high level of bromide in these waters, the major THMs 
formed were mixed bromochloro species (Figure 6). In addition, sub-pg/L levels of two 
iodinated THMs were detected in selected samples at plant 11, whereas pg/L levels of five 
iodinated THMs were detected at plant 12 (Figure 6). In addition to bromide in the source water, 
there was iodide as well. In other research, the formation of iodinated THMs was favored by 
chloramination, especially if the ammonia was added first, whereas the addition of chlorine first 
was found to favor the formation of the bromochloro species (Bichsel and von Gunten, 2000). 
Although the source water concentration of iodide was not measured in this study, the level of 
bromide in both source waters was comparable in March 2001. The difference in the formation 
of iodinated THMs at these two utilities may have been due to the order of addition of the 
chlorine and ammonia (chlorine first at plant 11, chlorine and ammonia together at plant 12). 

At plant 11, there was no significant seasonal variation in THM speciation (Figure 7). 
However, the formation of THM4 was highest in September 2001 when the water temperature 


97 












was the warmest (25°C) and was the lowest in February 2002 when the water temperature was 
the coldest (11°C). Likewise, there was a similar seasonal variation in iodinated THM formation 
(Figure 8), with more formation in September 2001 and less in March 2001 (18°C) and in 
February 2002. 


Figure 7. Seasonal formation and speciation Figure 8. Seasonal variations in iodinated 
of THMs at plant 11 effluent THM formation at plant 11 clearwell or 

plant effluent 



<0.5 or <1: Less than MRL (0.5 or 1.0 pg/L) 


3 02/11/2001 □ 11/05/2001~3 09/10/2001 D03/26/2001 



Trihalomethane (pg/L) 


At plant 12, because of the high level of bromide in this water in March 2001 (0.25 
mg/L) and February 2002 (0.33 mg/L), the major THMs formed were brominated species 
(Figure 9). Alternatively, in September 2001 the low level of bromide (0.02 mg/L) resulted in a 
shift to more highly chlorinated THMs (Figure 9). In addition, pg/L levels of five of the 
iodinated THMs were detected in these samples (Figure 10). The sixth iodinated THM, 
iodoform, was detected in only one sample (in the distribution system) in September 2001. The 
iodinated THMs formed included various combinations of chlorine, bromine, and iodide atoms. 
Similar to the THM4 speciation (Figure 9), as the level of bromide increased, the formation of 
dibromoiodomethane increased (from 1 to 4 pg/L), whereas the formation of 
dichloroiodomethane decreased (from 7-11 down to < 1 pg/L) (Figure 10). 


98 









































Figure 9. Impact of bromide on THM Figure 10. Seasonal variations in iodinated 

speciation at plant 12 effluent THM speciation at plant 12 effluent 



<0.5 or <1: Less than MRL (0.5 or 1 0 pg/L) 


Bromide (mg/L) 8 0.02 E3 0.15 B0.25 D0.33 


Dichloroiodomethane 


Bromochloroiodomethane 


Dibromoiodomethane 


Chlorodiiodomethane 


Bromide 

(mg/L) 


Bromodiiodomethane 


Iodoform 


<s- 

/> . 0 '° 

/ / 










1 

1 ~~ 1 



1 


! 





Q <0.5 



4 6 8 

Trihalomethane (pg/L) 


Haloacids. Chlorine dioxide/chlorine/chloramine disinfection at plant 11 resulted in the 
formation of 18-23 pg/L of the five regulated haloacetic acids (HAA5) in the plant effluent in 
March 2001, September 2001, November 2001, and February 2002. In addition, all nine HAAs 
(HAA9) were measured, which included all of the brominated HAA species. The levels of 
HAA9 in the plant effluents in March 2001, September 2001, November 2001, and February 
2002 at plant 11 were 42-49 pg/L. In March 2001, September 2001, November 2001, and 
February 2002, (chlorine dioxide and) chloramine disinfection at plant 12 resulted in the 
formation of 31-51 and 56-79 pg/L of HAA5 and HAA9, respectively, in the plant effluents. At 
these two plants, variations in bromide and disinfection practices impacted HAA formation and 
speciation (see discussion below). 

Because of the high level of bromide in these waters in March 2001, a major portion of 
the HAAs formed in the plant effluent and distribution system were the mixed bromochloro 
species (i.e., bromochloro-, bromodichloro-, and dibromochloroacetic acid) (Figure 11). At plant 
11 in March 2001, the formation of dihalogenated HAAs (DXAAs) was somewhat higher than 
the formation of the trihalogenated species (TXAAs) (Figure 12). The monohalogenated HAAs 
(MXAAs) were formed to a very low extent (as is found in other waters [Krasner et al., 1989]). 

A different pattern was observed at plant 12 in March 2001. At plant 12, the formation of 
DXAAs was significantly higher than the formation of TXAAs (Figure 12). 


99 



























Figure 11. March 26, 2001 


Effect of Bromide on HAA Speciation at Plants 11 and 12 in Simulated 
Distribution System Samples/Average Detention Time 


O) 





Figure 12. March 26, 2001 


Effect of Disinfection Scheme on HAA Speciation in Plant Effluents at 
Plant 11 (Chlorine Dioxide/Chlorine/Chloramines) 
and Plant 12 (Chloramines Only) 



MXAAs 


DXAAs 


TXAAs 


100 









































































In other research, chlorine dioxide (Zhang et al., 2000) and chloramines (Krasner et al., 
1996) have both been shown to produce little or no TXAAs, whereas DXAAs have been formed. 
The use of chloramines only at plant 12 did minimize TXAA formation much more than DXAA 
formation, whereas the formation of both types of HAAs at plant 11 was probably due to the 
presence of free chlorine in the clearwell. Because of the presence of a significant amount of 
THMs at plant 11, it is likely that most of the THMs and HAAs formed at this plant is due to the 
free chlorine usage. In other research, waters with relatively low levels of specific UV 
absorbance (SUVA) have formed more DXAAs than TXAAs (Hwang et al., 2000). The SUVA 
of the water at plant 11, especially at the point of disinfectant addition (i.e., 2.1 L/mg-m in March 
2001), was relatively low. It is likely that a combination of the disinfection scheme and natural 
organic matter of the water resulted in a higher formation of DXAAs than TXAAs at plant 11. 

Because of the higher level of bromide at plant 11 as compared to plant 12 in September 
2001, there was a greater shift to the formation of brominated HAAs at plant 11 than at plant 12 
(Figure 13). At both plants, there was 19-20 pg/L of TXAAs in the plant effluent (Figure 14), 
with the major difference for this DBP subclass being the bromine speciation (Figure 13). 
Alternatively, there was much more formation of DXAAs in the plant effluent at plant 12 than at 
plant 11 (55 versus 23 pg/L) (Figure 14). The change in bromide levels at plant 12—between 
March and September 2001—resulted in a shift in HAA speciation between chlorinated and 
brominated species (Figures 11 and 13). However, the relative formation of DXAAs and 
TXAAs was comparable in March and September 2001 at plant 12 (Figures 12 and 14), which 
was due to the use of chloramines only. 

Figure 13. 9/10/01 (plant 11 Br' = 0.21 mg/L, plant 12 Br‘ = 0.02 mg/L) 

Effect of Bromide and Disinfection Scheme on HAA Formation and 
Speciation in Plant Effluents at Plant 11 (Chlorine Dioxide/ 
Chlorine/Chloramines) and Plant 12 (Chloramines Only) 



101 

















Figure 14. September 10, 2001 


Effect of Disinfection Scheme on THM and HAA Formation and 
Speciation in Plant Effluents at Plant 11 (Chlorine Dioxide/ 
Chlorine/Chloramines) and Plant 12 (Chloramines Only) 



At plant 11 in November 2001, chlorine dioxide was initially dosed before the clarifier. 
No HAAs and essentially no THMs were detected from pre-disinfection with chlorine dioxide. 
At plant 11 in February 2002, chlorine dioxide was initially dosed at the clarifier. HAAs (5 and 
2 pg/L of dichloro- and trichloroacetic acid, respectively) were detected from pre-disinfection 
with chlorine dioxide. THM data for the filter influent sample were not reported due to quality 
control problems. However, the primary THM detected at that sample site was chloroform. At 
plant 11 in February 2002, after the addition of chlorine, significantly more THMs and HAAs 
were detected, which included the brominated species. It is possible that there was some DBP 
formation during the preparation of the chlorine dioxide solution, when the chlorine dioxide gas 
was dissolved in water. 

At plant 12 in February 2002, a significant level of HAA9 (32 pg/L) was produced 
during pre-treatment with chlorine dioxide disinfection, whereas very little THMs (3 pg/L) were 
formed. The majority of the HAAs produced were DXAAs (21 pg/L). These results are 
consistent with that of Zhang and colleagues (2000), in which chlorine dioxide was found to 
form very little THMs or TXAAs, but did form a significant amount of DXAAs. 

In addition to the target HAAs, several new brominated acids were identified by the 
broadscreen gas chromatography/mass spectrometry (GC/MS) methods (Tables 12 and 21). For 
example, 2,2-dibromopropanoic acid, dibromochloropropanoic acid, 3,3-dibromopropenoic acid, 
bromochloro-4-oxo-pentanoic acid, 3,3-dibromo-4-oxopentanoic acid, bromoheptanoic acid, 
bromochloroheptanoic acid, bromochlorononanoic acid, dibromoheptanoic acid, and cis-2- 
bromo-3-methylbutenedioic acid were identified (Table 12). Several of these bromo-acids were 


102 

























also seen in finished waters from plant 1 (EPA Region 9), and also in drinking waters from Israel 
that had been treated with chlorine or chlorine dioxide-chloramine (Richardson et al., submitted). 

At plant 12, in addition to the detection of brominated acids, five iodinated acids were 
detected (Table 21; mass spectra included in the Appendix). This represents the first time an 
iodo-acid has been identified as a DBP in drinking water. The identification of iodoacetic acid 
was confirmed through the analysis of an authentic standard (match of retention time and mass 
spectrum). Other identifications should be considered tentative until authentic chemical 
standards can be obtained to confirm them. However, high resolution mass spectrometry 
confirmed the presence of iodine in their structures, as well as their overall empirical formulas. 

In the case of iodobromoacetic acid, this assignment is very confident, due to only one isomer 
being possible. An attempt is currently being made to synthesize chemical standards for the 
remaining compounds to confirm their identities. 

Finally, target analysis carried out by UNC revealed the presence of 3,3- 
dichloropropenoic acid in finished water from plant 11 in September 2001 (Table 15). It was 
present at 0.7 pg/L in the finished water and remained stable in the distribution system. 3,3- 
Dichloropropenoic acid was also formed at plant 12 in September 2001 but was not detected in 
downstream locations (Table 16). 

Haloacetonitriles. In other DBP research, haloacetonitriles (HANs) have been found to 
be produced at approximately one-tenth the level (10 %) of the THMs (Oliver, 1983). A 
somewhat higher amount (on a relative basis) was detected in the plant 11 samples in March 
2001, and a somewhat lower amount was detected in September 2001. A somewhat higher 
amount (12 and 14 % in March and September 2001, respectively) was detected in the plant 12 
samples. 

Because of the high level of bromide in these waters in March 2001, brominated HANs 
predominated (Figure 15). Although plant 12 had somewhat more raw-water bromide than plant 
11 in March 2001, the shift in speciation to the more brominated HANs was greater in the plant 
11 samples. This may have been due, in part, to differences in the formation of brominated 
DBPs in the presence of chlorine (i.e., at plant 11) and in the presence of chloramines (i.e., at 
plant 12). In the presence of chlorine, bromide is oxidized to hypobromous acid, which is a very 
powerful halogenation agent. In the presence of chloramines, bromide can be converted to 
bromamines, which will not produce as much brominated DBPs as hypobromous acid. 


103 


Figure 15. March 26, 2001 


Effect of Bromide and Disinfection Scheme on HAN Speciation in 
Plants Effluents at Plant 11 (Chlorine Dioxide/Chlorine/Chloramines) 

and Plant 12 (Chloramines Only) 




Because of the higher level of bromide at plant 11 than plant 12 in September 2001, there 
was a significantly greater shift to the formation of brominated HANs at plant 11 than at plant 12 
that month (Figure 16). In addition to the formation of more of the brominated HANs in the 
Information Collection Rule (ICR) (e.g., dibromoacetonitrile) at plant 11, the target HAN 
dibromochloroacetonitrile was detected at plant 11 but not at plant 12 in September and 
November 2001. 

Chloroacetonitrile, another target HAN, was detected at both plants in September 2001 
(Figure 16) and November 2001. In addition, bromoacetonitrile was detected in one sample site 
per plant in September 2001. Dibromochloro- and tribromoacetonitrile—both brominated 
analogues of the ICR HAN trichloroacetonitrile—were detected at plant 11 in March 2001 by the 
broadscreen GC/MS methods (Table 12). 

Haloketones. In addition to the formation of low levels of haloketone (HK) compounds 
from the ICR (i.e., 1,1-dichloro- and 1,1,1-trichloropropanone), low levels of some of the target 
study HKs were detected in selected samples from plant 11 and plant 12 (Figure 17). In addition 
to the formation of the two chlorinated HKs in the ICR, brominated analogues of these two HKs 
(i.e., 1,1-dibromo- and l-bromo-l,l-dichloropropanone, respectively) were detected in 
September 2001 at plant 11, but were not detected at plant 12. In contrast, more of the 1,1,1,3- 
tetrachloropropanone was formed in September 2001 at plant 12. 


104 

















Haloacetonitrile (pg/L) 


Figure 16. September 10, 2001 


Effect of Bromide on HAN Speciation at 
Plant 11 (Br = 0.21 mg/L) and Plant 12 (Br' = 0.02 mg/L) 



Figure 17. September 10, 2001 

Effect of Bromide on HK Speciation in Plant Effluents at 
Plant 11 (Br' = 0.21 mg/L) and Plant 12 (Br' = 0.02 mg/L) 



105 
























































Figure 18 shows the impact of bromide on HK speciation at plant 12. In September 
2001, when the bromide level was low (0.02 mg/L), two chlorinated HKs (chloro- and 1,1,1,3- 
tetrachloropropanone) were detected that were not found in March 2001, November 2001, or 
February 2002. In March 2001 and February 2002, when the bromide level was high (0.25 and 
0.3 mg/L, respectively), two brominated HKs (1,1-bromopropanone [February 2002 only] and 1- 
bromo-l,l-dichloropropanone) were detected that were not found in September and November 
2001 (November bromide = 0.15 mg/L). 


Figure 18. Impact of bromide on HK speciation at plant 12 effluent 


<1: Less than MRL (1.0 (jg/L) 



Bromide 

(mg/L) 


In addition to the target HKs, other HKs were detected by the broadscreen GC/MS 
methods (Tables 12 and 21). Some of these HKs were analogous to the tri- and tetrahalogenated 
HKs analyzed by MWDSC, except they were mixed bromochloro species. In addition, another 
HK that was detected by the broadscreen GC/MS methods at plant 12 was pentachloropropanone 
(PCP). MWDSC analysts had attempted to include PCP in its target compound list, but it 
degraded immediately and completely in water under all conditions they evaluated (Gonzalez et 
al., 2000). 

Haloaldehydes. In addition to the formation of low levels of chloral hydrate 
(trichloroacetaldehyde), low levels of target haloacetaldehydes were detected (Figure 19). Both 
chlorinated and brominated species were formed. In March 2001, the level of chloral hydrate 
was higher at plant 11. In other research, chloramines were found to minimize the formation of 
chloral hydrate, whereas certain dihalogenated DBPs were formed to greater extents (Young et 
al., 1995). Consistent with that research, the formation of dihalogenated acetaldehydes was 
favored over trihalogenated species at plant 12. Moreover, the relative formation of di- versus 


106 












trihalogenated acetaldehydes at both utilities was consistent with the DXAA versus TXAA data 
at these plants (Figure 20). 


Figure 19. March 26, 2001 

Effect of Bromide and Disinfection Scheme on Haloacetaldehyde 
Speciation at Plant 11 (Chlorine Dioxide/Chlorine/Chloramines) and 
Plant 12 (Chloramines Only) in Distribution System Sample/Maximum 

Detention Time 



Figure 20. March 26, 2001 


Effect of Disinfection Scheme on HAA and Haloacetaldehyde 
Speciation in Plant Effluents at Plant 11 (Chlorine Dioxide/ 
Chlorine/Chloramines) and Plant 12 (Chloramines Only) 

■ Dihalogenated species □ Trihalogenated species 


100 % 


80% 


60% 


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0 % 



Haloacetaldehydes 

◄- Plant 11 


HAAs 

-► 


107 


Haloacetaldehydes 

-Plant 12- 


HAAs 

-► 



















































Figure 21 shows seasonal variations in the formation and speciation of haloacetaldehydes 
at plant 11. In September 2001, there was more of a shift to the brominated species. Also, 
because of the warmer water temperature in September 2001, there was the greatest 
haloacetaldehyde formation that month. Because of the colder water temperature in February 
2002, there was the lowest halaocetaldehyde formation that month. 

Figure 21. Seasonal formation and speciation of haloacetaldehydes at plant 11 clearwell or 
plant effluent 


<0.5: Less than MRL (0.5 ug/L) 


T ribromoacetaldehyde 


Chloral hydrate 


Bromochloroacetaldehyde 


Dichloroacetaldehyde 


102/11/2002 011/05/2001 *09/10/2001 003/26/2001 



0.2 


0.4 0.6 0.8 

Haloacetaldehyde (pg/L) 


1.2 


Figure 22 shows the impact of bromide on the formation and speciation of 
haloacetaldehydes at plant 12. In February 2002, when the level of bromide was the highest 
(0.33 mg/L), no dichloroacetaldehyde was detected, whereas there was bromochloroacetaldehyde 
formation. In addition, the formation of chloral hydrate (trichloroacetaldehyde) was low, 
whereas the formation of tribromoacetaldehyde was high. In March 2001 when the level of 
bromide was also high (0.25 mg/L), the formation of dichloro- and bromochloroacetaldehyde 
(both dihalogenated species) were similar and the amounts of the chloral hydrate and 
tribromoacetaldehyde (both trihalogenated species) were the same. Alternatively, in September 
2001 when the level of bromide was low (0.02) or in November 2001 when the level of bromide 
was moderate (0.15 mg/L), the formation of dichloroacetaldehyde was higher than that of 
bromochloroacetaldehyde and the formation of chloral hydrate was higher than that of 
tribromoacetaldehyde. Regardless of the level of bromide, the formation of dihalogenated 
species was typically favored over trihalogenated species (e.g., dichloroacetaldehyde versus 
chloral hydrate) at plant 12 (Figure 22). In February 2002 (bromide = 0.33 mg/L), 


108 


























dichloroacetaldehyde was not detected with an minimum reporting level (MRL) of 0.98 pg/L. 

As a result, the sum of the dihalogenated species was relatively low that month. In addition, that 
was the only month in which chlorine dioxide was used during pre-treatment. 

In addition to the target haloacetaldehydes, other haloaldehydes were detected by the 
broadscreen GC/MS methods (Tables 12 and 21). At plant 11, dibromo- and 
bromodichloroacetaldehyde—which are brominated analogues of dichloroacetaldehyde and 
chloral hydrate, respectively—were detected. In addition, another brominated aldehyde 
(2-bromo-2-methylpropanal) was detected at both plants. 

Halonitromethanes. In March 2001, September 2001, November 2001, and February 
2002, sub-pg/L levels of chloropicrin (trichloronitromethane) and other halonitromethanes were 
detected in selected samples at plant 11 (bromopicrin was detected at 1 pg/L in one sample in 
February 2002). This included mono-, di-, and trihalogenated species, with and without 
bromine. Sub-pg/L to low pg/L levels of halonitromethanes were detected at plant 12 in March 
2001, September 2001, November 2001, and February 2002. 


109 


Figure 22. Impact of bromide on haloacetaldehyde speciation at plant 12 effluent 


Bromide (mg/L) 


□ 0.02 E30.15 10.25 D0.33 


T ribromoacetaldehyde 


Chloral hydrate 


Bromochloroacetaldehyde 


Dichloroacetaldehyde 



0 0.5 1 1.5 2 2.5 3 3.5 4 


Haloacetaldehyde (Mg/L) 


Figure 23. Haloacetaldehyde speciation at plant 12 effluent 


*Dichloroacetaldehyde not detected with MRL of 0.98 pg/L 


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100 % 

80% 

60% 

40% 

20 % 

0 % 


Dihalogenated 
% of Halo- Trihalogenated 
acetaldehydes % of Halo- 
acetaldehydes 


0.15 


0.02 


0.33 


0.25 


Bromide 

(mg/L) 


110 














































Figure 24 shows the impact of bromide on the speciation of the halonitromethanes at 
plant 12. As bromide increased, the formation of chloropicrin decreased (from 0.9 down to 0.2- 
0.4 pg/L), whereas the formation of the brominated species increased (e.g., 
bromochloronitromethane formation increased from not detected or 0.2 to 0.7 or <1 pg/L). In 
February 2002, when the level of bromide was the highest (0.33 mg/L), bromonitromethane was 
detected, but not in other months. In addition, dibromonitromethane was only detected in 
February 2002 and in March 2001 (bromide = 0.25 mg/L). In addition to the formation of 
chloropicrin, brominated analogues of this trihalogenated nitromethane were detected in the 
September 2001, November 2001, and February 2002 samples. Data for the brominated 
trihalogenated nitromethanes were not available (N/A) in the March 2001 samples. Bromopicrin 
was detected in September 2001 (bromide = 0.02 mg/L) in the filter influent sample, but was not 
detected in the plant effluent sample, whereas the two mixed bromochloro trihalogenated species 
were detected in the plant effluent. Alternatively, when bromide was higher (in November 2001 
[0.15 mg/L) and February 2002), bromopicrin formation was the highest (2 and 5 pg/L, 
respectively). 

Figure 24. Impact of bromide on halonitromethane speciation at plant 12 effluent 


<1: Less than MRL (1.0 pg/L); N/A= Not analyzed in March 2001 when bromide = 0.25 mg/L; 
*Bromodichloronitromethane not detected in Feb. 2002 (Br = 0.33 mg/L) with MRL of 2.0 pg/L 



0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 

Halonitromethane (Mg/L) 


At plant 11 in September 2001, bromodichloro- and dibromochloronitromethane were 
detected at or above the MRL of 0.5 pg/L in the SDS sample held for maximum detention time. 
Although the SDS samples were not kept cold during the prolonged shipping period in 
September 2001, these results suggest that these compounds may have been present in other 
plant 11 samples, but at concentrations below the MRL. 


Ill 



































Halogenatedfuranones. Tables 17 and 18 show the results for halogenated furanones in 
the September 2001 samplings for plants 11 and 12; Tables 26 and 27 show the results for the 
February 2002 samplings. Data are included for 3-chloro-4-(dichloromethyl)-5-hydroxy-2[5H]- 
furanone, otherwise known as MX; (E)-2-chloro-3-(dichloromethyl)-4-oxobutenoic acid, 
otherwise known as EMX; (Z)-2-chloro-3-(dichloromethyl)-4-oxobutenoic acid (ZMX); the 
oxidized form of MX (Ox-MX); brominated forms of MX and EMX (BMXs and BEMXs); and 
mucochloric acid (MCA), which can be found as a closed ring or in an open form. Results are 
displayed graphically in Figures 25 and 26. 

Many sample points were analyzed in the EPA Region 6 plants (9/10/01), clearly 
showing that CIO 2 at plant 11 did not produce MX and MX-analogues at the filter influent except 
for 20 ng/L of BEMX-1, and that intermediate chlorination/post-chloramination at plant 11 
produced more MX-analogues than chloramines at plant 12. ZMX was detected (90 ng/L) in the 
plant 11 clearwell effluent, but was not detected in the plant effluent, whereas MX was the same 
at both sample sites (20 ng/L). Predisinfection with CIO 2 at plant 11 did not appear to effectively 
remove precursors of MX-analogues as has been observed for predisinfection with ozone for 
other treatment plants in this study. A significant higher concentration of MX (853 ng/L) was 
detected in the plant 11 DS/average sample compared to the PE sample (20 ng/L), whereas the 
BEMX-3 was detected in the PE (200 ng/L) and not in the DS/average sample. The plant 11 
SDS/maximum sample (490 ng/L BEMX-3) shows that BEMX-3 was stable under the 
conditions employed in the SDS test. These results suggest that the DS/average sample may 
represent a different water than the PE sample, as these samples were not collected to follow a 
“plug” of water over time (as the SDS test was set up to do). With a bromide concentration of 
0.21 mg/L and TOC concentration of 3.5 mg/L, the raw water for plant 11 produced BMX 
compounds during intermediate chlorination/post-chloramination, as found in the majority of 
samples (11-490 ng/L) from plant 11. Due to the difference in water quality of the river basin in 
September 2001 (0.02 mg/L Br- and 7.5 mg/L TOC), which fed plant 12, and the difference in 
disinfection (chloramines only), substantially less brominated MX-analogues (17-90 ng/L) were 
produced relative to plant 11. At plant 11, the major production of BMX-analogues occurred in 
the clearwell influent after intermediate chlorination, whereas at plant 12, it occurred between 
the filter effluent and plant effluent samples. 

In the second sampling of the EPA Region 6 plants (2/11/02 or 2/12/02) for halogenated 
furanones, MX and a chlorinated MX-analogue, MCA, were more predominant at plants 11 and 
12 than in the earlier sampling (September 2001). One BMX analogue, BMX-1, was also 
formed at 80 and 60 ng/L in finished waters from plants 11 and 12, respectively, but was not 
detectable in the DS/maximum samples. The raw water quality of plant 11 was not that different 
in February 2002 (0.18 mg/L of bromide and 4.3 mg/L of TOC), whereas plant 12’s was 
significantly different (0.33 mg/L bromide and 5.3 mg/L of TOC). In addition, plant 12 used 
chlorine dioxide during pretreatment in February 2002. These changes in the distribution and 
occurrence levels of the MX-analogues may be due to changes in raw water quality and 
operational (treatment/disinfection) parameters from Fall 2001 to Winter 2002. 


112 


Halogenated Furanone Concentration (|jg/L) 


Figure 25. Halofuranone data at EPA Region 6 plants (9/10/01) 

EPA Region 6 (9/10/01) 


HBMX-1 

■ BEMX-1 

■ BMX-2 

□ BEMX-2 

■ BMX-3 1BEMX-3 

■ MX 

G3EMX 

□ ZMX 

□ MCA (ring) 

□ MCA (open) 


1.20 

1.00 

0.80 

0.60 

0.40 

0.20 

0.00 



Rant 11 


Rant 12 


Sampling Sites 


113 















































































Figure 26. Halofuranone data at EPA Region 6 plants (2/11/02 or 2/12/02) 


EPA Region 6 (2/11/02 or 2/12/02) 


□ BMX-1 □ BEMX-1 ■ BMX-2 ■ BEMX-2 BBMX-3 DBEMX-3 

■ MX BEMX HZMX □ MCA (ring) 11 MCA (open) □ Ox-MX 


j 0.18 

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Plant 11 



PE 

Dual Media Filters 
+CI02+CI2+NH3 


DS/max 


FI PE 

CI02+CI2+NH3 I Filter+CI2+NH3 


DS/max 


Plant 12 


Sampling Points 


Other Halogenated DBPs. In target analyses conducted at UNC, haloamides were 
frequently identified in finished waters from plants 11 and 12 (Tables 15-16, 24-25). In samples 
taken in February 2002, all five target haloamides were identified: monochloroacetamide, 
monobromoacetamide, dichloroacetamide, dibromoacetamide, and trichloroacetamide. 
Concentrations of individual species ranged from 0.4 to 2.8 pg/L in the plant effluent and were 
comparable in the distribution system. In September 2001, only one haloacetamide was 
targeted—dichloroacetamide, which was found at 2.8 and 5.6 pg/L in finished waters from 
plants 11 and 12, respectively. Haloamides have not been a class of DBPs quantified in potable 
waters previously. Because the levels observed in these samples are similar to other DBPs that 
are commonly measured, this may be an important class of DBP that warrants further study. 

A few additional halogenated DBPs were identified by broadscreen GC/MS analysis, 
including dibromoaniline, dibromodichloroaniline, and tribromochloroaniline (plant 12 finished 
water, November 2001). These compounds were not present in the raw, untreated water. 

Volatile Organic Compounds. Carbon tetrachloride was detected in two samples at plant 
11 (clearwell and plant effluent) in March 2001 at sub-pg/L levels. Carbon tetrachloride is a 
volatile organic compound (VOC) and a possible DBP. Carbon tetrachloride has been detected 
by some utilities in gaseous chlorine cylinders (EE&T, 2000). Incidents of carbon tetrachloride 
contamination of chlorine cylinders have been traced to either imperfections in the 
manufacturing process or improper cleaning procedures. Carbon tetrachloride is used to clean 


114 














































































out cylinders before filling with chlorine. If carbon tetrachloride is not allowed sufficient time to 
evaporate, it can contaminate the chlorine. 

Methyl ethyl ketone (MEK) was detected in the raw water, in the distribution system, and 
in SDS testing at plant 11 on September 10, 2001 at a concentration of 0.6-0.7 pg/L. MEK was 
not detected at or above the MRL of 0.5 pg/L in the clearwell effluent or the plant effluent. 

MEK was detected at the filter influent and in the distribution system of plant 12 on September 
10, 2001 at a concentration of 0.6 pg/L. MEK was not detected at or above the MRL in the raw 
water or the plant effluent. MEK is an industrial solvent and a possible DBP. At plant 11, its 
presence in the distribution system was most likely due to its low-level occurrence in the raw 
water. At plant 12, its occurrence in some samples slightly above the MRL does not allow for a 
determination as to its origin. 

Non-Halogenated DBPs. A few non-halogenated DBPs were detected in treated waters 
from plants 11 and 12 (Tables 15-16, 24-25). The finding of 6-hydroxy-2-hexanone in the filter 
influent (at 0.8 pg/L) of plant 11 represented one of the few times this DBP was identified in this 
study (September 2001, Table 15). This compound was likely formed by the initial treatment 
with chlorine dioxide. 6-Hydroxy-2-hexanone has also been previously reported as an ozone 
DBP (Richardson et al., 1999). However, although it was initially formed, it was not present in 
the plant effluent (finished water). Because plant 11 did not use GAC or biofiltration, it was 
probably not removed by the filtration process. Many ketones can undergo base-catalyzed 
hydrolysis or can react with chlorine to form secondary by-products. Either phenomenon may be 
responsible for the loss of this DBP. Another DBP that is typically an ozone DBP— 
dimethylglyoxal—was also found in the finished water from both plants 11 and 12, generally at 
levels between 1 and 3 pg/L in the plant effluent. Zhang and colleagues (2000) demonstrated 
that other disinfectants/oxidants can form carbonyl containing compounds. Broadscreen GC/MS 
analysis also revealed the presence of acetone and glyoxal in finished water from plant 12 
(November 2001), as well as several non-halogenated carboxylic acids in the finished waters, 
which were at significantly higher concentrations than in the raw, untreated water. 

Distribution System Issues. Because plant 11 used chloramines in the distribution 
system, most of the DBPs were found to not increase significantly in concentration in SDS 
testing (Figure 27) or in the distribution system. Many non-THM DBPs (e.g., 
dichloroacetonitrile, 1,1,1-trichloropropanone, chloral hydrate) are known to degrade at high pH 
(Stevens et al., 1989; Croue and Reckhow, 1989). Because the distribution system and SDS 
testing in March 2001 was only at a pH of 7.4-7.6, most non-THM DBPs were found to be 
relatively stable (Figure 27). 


115 


Figure 27: March 26, 2001 


Effect of Simulated Distribution System Testing at Plant 11 on 
Formation and Stability of DBPs in Chloraminated Water at pH 7.4-7.6 


■ Plant Eff □ SDS/Ave USPS/Max 




Figure 28 shows a comparison of SDS testing and distribution-systems samples to the 
plant effluent for the THMs for plant 12 for March 2001. Because plant 12 used chloramines, 
THMs would not be expected to increase significantly in concentration in the distribution system 
or in SDS testing. THM4 concentration did increase in the plant 12 SDS testing (from 34 pg/L 
in the plant effluent to 38 and 49 pg/L in the SDS samples held for average and maximum 
detention times, respectively). The increase in concentration in the SDS samples (especially at 
maximum detention time) was primarily due to the formation of the brominated THMs (Figure 
28). Other research has shown that THM formation can increase in chloraminated water when 
an elevated level of bromide is present (Diehl et al., 2000). 


116 






























































Figure 28. March 26 , 2001 


Comparison of SDS Testing and Distribution-System Samples 
to Plant 12 Effluent for the THMs 


□ Plant Eff H SDS/Ave □ SDS/Max m DS/Ave ■ DS/Max 



Dichloroiodomethane Not Reported (NR) for SDS/Max and DS/Max 
and Bromochloroiodomethane NR for DS/Max 


TIFT 



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Alternatively, THM4 was significantly higher in concentration in the plant 12 
distribution-system samples in March 2001 (34 pg/L in the plant effluent versus 52 and 84 pg/L 
in the distribution-system samples collected at average and maximum detention times, 
respectively). The increase in concentration in the distribution-system samples (especially at 
maximum detention time) was primarily due to the formation of dibromochloromethane and 
bromoform (Figure 28). Distribution-system samples can be significantly different than the plant 
effluent for two reasons: 

♦ One, grab samples for the plant and distribution system were collected on the same day 
(as requested) rather than following a plug of water over time-i.e., collecting the plant effluent 
on one day and collecting the distribution-system samples a period of time (e.g., days) later that 
matched the expected detention time in the system. Thus, the distribution-system samples 
(especially at maximum detention time) represented water produced at the plant on a different 
day in which the source-water quality and/or plant operations may have been different. 

♦ Second, distribution-system samples may not always contain water only from the plant 
effluent if there are other sources of water that may feed the distribution system (e.g., well 
water). 

♦ Thus, distribution-system samples represented the actual occurrence of DBPs, whereas 
SDS testing allowed for an examination of the effect of detention time on DBP formation 
without any of the confounding issues associated with distributed water. 

In terms of the iodinated THMs at plant 12 in March 2001, SDS results were comparable 
to the plant effluent data. Alternatively, some of the iodinated THMs (i.e., 


117 







































































bromochloroiodomethane, dibromoiodomethane, and bromodiiodomethane) were significantly 
higher in the distribution system at average detention time as compared to the plant effluent and 
one of the iodinated THMs (i.e., dibromoiodomethane) was significantly lower in the distribution 
system at maximum detention time (Figure 28). Because a similar increase or decrease in 
formation was not observed in the SDS testing, this suggests that the distribution-system samples 
represented a somewhat different source of water than the plant effluent collected on the same 
day. 


Figure 29 shows the effect of SDS testing at plant 12 in March 2001 on the formation and 
stability of a range of DBPs. Because the SDS testing was only at a pH of ~8, most non-THM 
DBPs were found to be relatively stable (Figure 29). 


Figure 29. March 26, 2001 

Effect of Simulated Distribution System Testing at Plant 12 on 
Formation and Stability of DBPs in Chloraminated Water at pH ~8 


I Plant Eff □ SDS/Ave BSDS/Max 


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118 
































































REFERENCES 


Aieta, E. M., and J. D. Berg. A review of chlorine dioxide in drinking water treatment. Journal 
of the American Water Works Association 78(6):62 (1986). 

American Public Health Association (APHA/ Standard Methods for the Examination of Water 
and Wastewater, 20th ed. APHA, American Water Works Association, and Water Environment 
Federation: Washington, DC (1998). 

Bichsel, Y., and U. von Gunten. Formation of iodo-trihalomethanes during disinfection and 
oxidation of iodide-containing waters. Environmental Science & Technology 34(13):2784 
( 2000 ). 

Bolyard, M., P. S. Fair, and D. P. Hautman. Occurrence of chlorate in hypochlorite solutions 
used for drinking water disinfection. Environmental Science & Technology 26(8): 1663 (1992). 

Croue, J.-P., and D. A. Reckhow. Destruction of chlorination byproducts with sulfite. 
Environmental Science & Technology, 23(11): 1412 (1989). 

Diehl, A. C., G. E. Speitel Jr., J. M. Symons, S. W. Krasner, C. J. Hwang, and S. E. Barrett. 

DBP formation during chloramination. Journal of the American Water Works Association, 
92(6):76 (2000). 

Environmental Engineering & Technology, Inc. (EE&T). Occurrence of, and Problems 
Associated With, Trace Contaminants in Water Treatment Chemicals. Progress report to 
AWWA Research Foundation, Denver, CO, 2000. 

Gonzalez, A. C., S. W. Krasner, H. Weinberg, and S. D. Richardson. Determination of newly 
identified disinfection by-products in drinking water. Proceedings of the American Water Works 
Association Water Quality Technology Conference, American Water Works Association: 

Denver, CO, 2000. 

Hwang, C. J., M. J. Sclimenti, and S. W. Krasner. Disinfection by-product formation reactivities 
of natural organic matter fractions of a low-humic water. In Natural Organic Matter and 
Disinfection By-Products: Characterization and Control in Drinking Water (S. E. Barrett, S. W. 
Krasner, and G. L. Amy, eds.), American Chemical Society: Washington, D.C., pp. 173-187, 
2000 . 

Krasner, S. W., M. J. McGuire, J. G. Jacangelo, N. L. Patania, K. M. Reagan, and E. M. Aieta. 
The occurrence of disinfection by-products in U.S. drinking water. Journal of the American 
Water Works Association 81(8):41 (1989). 

Krasner, S. W., J. M. Symons, G. E. Speitel, Jr., A. C. Diehl, C. J. Hwang, R. Xia, and S. E. 
Barrett. Effects of water quality parameters on DBP formation during chloramination. 


119 


Proceedings of the American Water Works Association Annual Conference, Vol. D, pp. 601-628, 
American Water Works Association: Denver, CO, 1996. 

Oliver, B. G. Dihaloacetonitriles in drinking water: algae and fulvic acid as precursors. 
Environmental Science & Technology 17(2):80 (1983). 

Richardson, S. D., A. D. Thruston, Jr., T. V. Caughran, P. H. Chen, T. W. Collette, T. L. Floyd, 
K. M. Schenck, and B. W. Lykins, Jr. Identification of new ozone disinfection by-products in 
drinking water. Environmental Science & Technology 33:3368 (1999). 

Richardson, S. D., A. D. Thruston, Jr., C. Rav-Acha, L. Groisman, I. Popilevsky, O. Juraev, V. 
Glezer, A. B. McKague, M. J. Plewa, and E. J. Wagner. Tribromopyrrole, brominated acids, and 
other disinfection byproducts produced by disinfection of drinking water rich in bromide. 
Environmental Science & Technology (submitted). 

Young, M. S., D. M. Mauro, P. C. Uden, and D. A. Reckhow. The formation of nitriles and 
related halogenated disinfection by-products in chlorinated and chloraminated water; application 
of microscale analytical procedures. Preprints of papers presented at 210th American Chemical 
Society (ACS) National Meeting, Chicago, IL, American Chemical Society: Washington, D.C., 
pp. 748-751, 1995. 

Stevens, A. A., L. A. Moore, and R. J. Miltner. 1989. Formation and control of non- 
trihalomethane disinfection by-products. Journal of the American Water Works Association , 
81(8):54 (1989). 

Zhang, X., S. Echigo, R. A. Minear, and M. J. Plewa. Characterization and comparison of 
disinfection by-products of four major disinfectants. In Natural Organic Matter and 
Disinfection By-Products: Characterization and Control in Drinking Water (S. E. Barrett, S. W. 
Krasner, and G. L. Amy, eds.), pp. 299-314, American Chemical Society: Washington, D.C., 
2000. 


120 


EPA REGION 4: PLANTS 7 AND 8 


Plant Operations and Sampling 

On December 11, 2000, March 12, 2001, September 24, 2001, and January 14-16, 2002, 
plants 7 and 8 (in EPA Region 4) were sampled. 

Plant 7 is an ozone plant (Figure 1). The raw water was first treated with chloramines. 
The water was then lime-softened and filtered. The filtered water was ozonated. The ozonated 
water was chlorinated, stored, and distributed. 

Figure 1 

Plant 7 Schematic 



Plant 8 is a membrane plant (Figure 2). This plant consisted of two facilities operating 

simultaneously and parallel to one another; a portion of the water was treated with membranes: 

• In the lime softening portion of the plant, the raw water was treated with chlorine. The water 
was then lime-softened. The softened water was chloraminated, filtered, and stored. 

• In the membrane-softening portion of the plant, the pH of the raw water was adjusted with 
sulfuric acid. The acidified water was filtered and treated with membranes (TFC®-S 
polyamide, Koch Membrane Systems; softening, low pressure for brackish water treatment 
membrane elements). The membrane-treated water was chlorinated and passed through an 
adsorber and stripper towers. The pH of the water was adjusted with sodium hydroxide and 
mixed with the lime-softened water. 

The combined treated waters were chloraminated, stored, and distributed. 


121 















Figure 2 

Plant 8 Schematic 


Lime Softening 

Train 


Coagulation and 
Floculation 



Filtration 


Clearwell 


ammonia 


Raw Water 

chlorine 
polymer 
lime 

chlorine 

ammonia 


NaOFF 

chlorine 


Membrane 
Softening Train 

FLSCL 



Cartridge 

Filters 


Membranes 


chlorine 


Clearwell 


Distribution <- 


Adsorber/ 
Stripper Towers 

- 

Ground 
Storage 


Plant 7 was sampled at the following locations: 

(1) raw water 

(2) settled water 

(3) filter effluent 

(4) effluent of the ozone contactor 

(5) the plant effluent 

In addition, plant effluent was collected and simulated distribution system (SDS) testing was 
conducted (a 24-hr holding time was typically used [27-hr in January 2002]). Furthermore, the 
distribution system was sampled at a location that receives water from plant 7 and from another 
treatment plant. 

Plant 8 was sampled at the following locations: 

(1) raw water 
Lime Softening 

(2) settled water 

(3) filter effluent 
Membrane Softening 

(4) membrane effluent 

(5) effluent of the stripper towers 
Combined Treated Waters 


122 



































( 6 ) the plant effluent 

In addition, plant effluent at plant 8 was collected and SDS testing was conducted (a 24-hr 
holding time was typically used [22.5 h in September 2001]. Furthermore, the distribution 
system of plant 8 was sampled at one location. 

On the day of sampling, information was collected on the operations at each plant 
(Tables 1-2). 


Table 1. Operational information at plant 7 


Parameter 

12 / 11/00 

3/12/01 

9/24/01 

1/14/02 

Plant flow (mgd) 

8.7 

9.0 

9.6 

13.6 

Total chlorine dose at plant influent (mg/L as CI 2 ) 

13 

10 

5 

5.3 

Chlorine dose at influent pipe or raw standpipe 
(mg/L as CI 2 ) 

3.0 

7.0 

2 

2 

Chlorine dose at treatment unit collector ring or 
basin effluent (mg/L as CI 2 ) 

7.0 

3.0 

3 

3.3 

Ammonia dose at plant influent (mg/L as NH 3 -N) 

1.1 

1.1 

0.94 

1.3 

Lime dosage (mg/L) 

219 

225 

230 

243 

Polymer dosage (mg/L) 

0.2 

0.2 

0.2 

0.2 

CO 2 dosage (mg/L) 

8.3 

4.0 

10 

3.6 

Ozone dose (mg/L) 

6.4 

5.0 

4 

7.4 

Hydraulic retention time in ozone contactor (min) 

25 

20 

30 

20 

CT achieved from ozonation (mg/L-min) 

NA a 

NA 

NA 

0.37 

Chlorine dose at ozone contactor eff. (mg/L as CI 2 ) 

3.1 

3.0 

6.0 

6.7 


a NA = Not available 


Table 2. Operational information at plant 8 


Parameter 

12 / 11/00 

3/12/01 

9/24/01 

1/16/02 

Overall plant flow (mgd) 

11.05 

11.41 

10.1 

11.64 

Plant flow for lime softening (mgd) 

4.5 

3.0 

3.3 

3.00 

Plant flow for membrane softening (mgd) 

6.55 

8.41 

6.8 

8.64 

Lime Softening 





Chlorine dose at lime softening inf. (mg/L as CI 2 ) 

6.0 

6.0 

8.0 

8 

Lime dosage (mg/L) 

205 

225 

215 

225 

Polymer dosage (mg/L) 

0.05 

0.05 

0.025 

0.025 

Chlorine dose at filter influent (mg/L as CI 2 ) 

12 

12 

12 

12 

Ammonia dose at filter influent (mg/L as NH 3 -N) 

1.0 

1.0 

1.0 

1 

Membrane Softening 





H 2 SO 4 dose at membrane softening inf. (mg/L) 

180 

180 

134 

182 

Operating pressure (psi) 

118 

118 

118 

118 

Chlorine dose at membrane effluent (mg/L as CI 2 ) 

2.6 

2.6 

2.6 

1.8 

NaOH dose at stripper tower effluent (mg/L) 

16.6 

62 

16 

26 

Chlorine dose at stripper tower eff. (mg/L as CI 2 ) 

7.1 

7.1 

7.5 

6.5 

Combined Treated Waters 





Ammonia dose at plant effluent (mg/L as NH 3 -N) 

1.0 

1.0 

1.0 

NA 


123 











































Water Quality 

On the day of sampling, information was also collected on water quality at each plant 
(Tables 3-4). Data were collected for total organic carbon (TOC) and ultraviolet (UV) 
absorbance for plant 7 and plant 8 (Table 5). Plants 7 and 8 treated a groundwater that was high 
in TOC (12-13 mg/L) and in color. Lime softening at plant 7 and plant 8 removed 21-35 % of 
the TOC and reduced the UV by 38-48 %. Filtration removed another 3-9 % of the TOC. At 
plant 7, ozonation did not significantly effect the level of TOC, whereas the UV was reduced by 
another 13-37 %. The overall (cumulative) removal of TOC at plant 7 (due to lime softening, 
filtration, and ozonation) was 27-33 % and the UV was reduced by 52-61 %. The overall 
(cumulative) removal of TOC at plant 8 in the lime-softening portion of the plant was 29-39 % 
and the UV was reduced by 43-54 %. At plant 8, the membrane process reduced both the TOC 
and the UV by 97-98 %. At plant 8, the plant effluent TOC was 2.5-3.6 mg/L, which 
approximately matched the relative contributions of TOC from each of the two portions of the 
plant. The concentration of TOC (2.6-3.5 mg/L) in the distribution system of plant 8 confirmed 
that this location was receiving membrane treated water. 

Table 6 shows the values of miscellaneous other water quality parameters in the raw 
water of plants 7 and 8. The raw water at each plant contained a moderate or high amount of 
bromide (the bromide concentrations at plant 7 and plant 8 were 0.12-0.14 and 0.25-0.33 mg/L, 
respectively). At plant 8, a significant percentage (60-67 %) of the raw-water bromide was 
rejected by the membrane process. 

The raw water also contained a moderate amount of ammonia (0.5-0.7 mg/L as N). It 
takes 7.6 mg/L of chlorine to breakpoint chlorinate 1.0 mg/L of ammonia-nitrogen. Ground- 
waters that are high in ammonia are often high in hydrogen sulfide (Krasner et al., 1996), which 
also exerts a high chlorine demand. When chlorine is added to such groundwaters, typically 
chloramines are formed, since not all of the ammonia will be breakpoint chlorinated. At plant 8, 
chloramines were formed during the chlorination of the raw water at the lime-softening portion 
of the plant and during the chlorination of the membrane effluent (Table 4). 

DBPs 


Oxyhalides. At plant 7, ozonation did not result in the formation of bromate at or above 
the minimum reporting level (MRL) of 3 pg/L. Ammonia addition is a method of controlling 
bromate formation, because the ammonia may be able to tie up the bromide as bromamines 
(Krasner et al., 1993). At plant 7, 0.9-1.3 mg/L of ammonia-nitrogen was added to the raw water 
in addition to the 0.6-0.7 mg/L that was naturally present. Ozonation of a water with a free 
chlorine residual can result in the formation of chlorate. Chlorate was not detected at plant 7, 
since the free chlorine was converted to chloramines by the ammonia present prior to the 
addition of ozone. 


124 


Table 3. Water quality information at plant 7 



pH 

Temperature (°C) 

Disinfectant Residual 3 (mg/L) 

Location 

12/11/00 

3/12/01 

9/24/01 

1/14/02 

12/11/00 

3/12/01 

9/24/01 

1/14/02 

12/11/00 

3/12/01 

9/24/01 

1/14/02 

Raw water 

7.1 

7.35 

7.3 

7.30 

25 

25 

25 

25 

— 

— 

— 

— 

Settled 

9.75 

9.59 

10.1 

10.09 

25 

25 

25 

25 

2.5 

— 

0.6 

ND b 

Filter eff. 

9.60 

9.51 

9.8 

9.96 

25 

25 

25 

25 

1.4 

3.6 

0.4 

0.9 

Ozone eff. 

9.23 

9.24 

9.4 

9.55 

25 

25 

25 

25 

>0.9 

2.7 

trace 

1.0 

Plant eff. 

8.95 

8.91 

9.0 

9.07 

25 

25 

25 

25 

5.0 

4.8 

4.9 

4.7 

Dist. syst. 

8.98 

8.95 

9.0 

9.08 

25 

25 

25 

25 

4.4 

3.6 

4.6 

4.1 

SDS 

NA 

NA 

NA 

9.07 

NA 

NA 

NA 

25 

NA 

NA 

NA 

4.7 


“Chloramine residuals 
‘’ND = Not detected 


Table 4. Water quality information at plant 8 



pH 


Temperature (°C) 

Disinfectant Residual 3 (mg/L) 

Location 

12/11/00 

3/12/01 

9/24/01 

1/14/02 

12/11/00 

3/12/01 

9/24/01 

1/14/02 

12/11/00 

3/12/01 

9/24/01 

1/14/02 

Raw water 

7.05 

7.02 

7.2 

7.19 

24.8 

24.8 

24.6 

24.2 

— 

— 

— 

— 

Lime Softening 

Settled 

9.7 

10.4 

NA 

10.52 

24.4 

25.0 

NA 

23.9 

1.1 

0.4 

NA 

1.6 

Filter eff. 

9.2 

10.0 

10.2 

10.16 

25.6 

25.3 

24.8 

23.9 

5.0 

3.5+ 

5.9 

3.5+ 

Membrane Softening 

Memb. eff 

5.5 

5.38 

5.4 

5.55 

25.0 

25.4 

23.8 

24.4 

— 

— 

— 

— 

Stripper 
tower eff. 

8.1 

7.30 

9.1 

6.81 

25.0 

25.2 

24.2 

25.1 

5.5 

3.5+ 

4.7 

3.5+ 

Combined Treated Waters 

Plant eff. 

8.8 

8.93 

9.0 

8.75 

25.0 

26.7 

24.3 

25.1 

4.1 

3.5+ 

4.6 

3.5+ 

Dist. syst. 

8.8 

8.90 

9.0 

8.95 

25.0 

25.5 

24.9 

25.0 

4.1 

4.0 

4.5 

4.2 

SDS 

8.7 

NA 

8.8 

8.8 

23.5 

NA 

23.0 

24.2 

3.7 

NA 

4.3 

4.0 


“Chloramine residuals 


125 

























































































Table 5. TOC and UV removal at plants 7 and 8 


Location 

TOC 

(mg/L) 

UV a 

(cm 1 ) 

SUVA b 

(L/mg-m) 

Removal/Unit (%) 

Removal/Cumulative (%) 

Flow 

TOC 

UV 

TOC 

UV 

(mgd) 

12/11/2000 









Plant 7 Raw 

12.7 

0.470 

3.70 

— 

— 

— 

— 


Plant 7 Settled 

9.21 

0.277 

3.01 

27% 

41% 

27% 

41% 


Plant 7 Filter Eff. 

8.85 

0.282 

3.19 

3.9% 

-1.8% 

30% 

40% 


Plant 7 Ozone Eff. 

8.55 

0.211 

2.47 

3.4% 

25% 

33% 

55% 


Plant 7 Dist. Syst. 

7.87 








Plant 8 Raw 

13.4 

0.505 

3.77 

— 

— 

— 

— 


Plant 8 Settled 

8.7 

0.262 

3.01 

35% 

48% 

35% 

48% 


Plant 8 Filter Eff. 

8.13 

0.233 

2.87 

6.6% 

11% 

39% 

54% 

4.5 

Plant 8 Membrane Eff. 

0.42 

0.01 

2.38 

97% 

98% 

97% 

98% 

6.55 

Plant 8 Plant Eff./Measured 

3.55 







11.05 

Plant 8 Plant Eff./Predicted c 

3.56 








Plant 8 Dist. Syst. 

3.47 








3/12/2001 









Plant 7 Raw 

12.3 

0.458 

3.72 

— 

— 

— 

— 


Plant 7 Settled 

9.28 

0.283 

3.05 

25% 

38% 

25% 

38% 


Plant 7 Filter Eff. 

8.96 

0.283 

3.16 

3.4% 

0% 

27% 

38% 


Plant 7 Ozone Eff. 

8.52 

0.179 

2.10 

4.9% 

37% 

31% 

61% 


Plant 7 Dist. Syst. 

8.42 








Plant 8 Raw 

12.8 

0.494 

3.86 

— 

— 

— 

— 


Plant 8 Settled 

8.84 

0.267 

3.02 

31% 

46% 

31% 

46% 


Plant 8 Filter Eff. 

8.44 

0.248 

2.94 

4.5% 

7.1% 

34% 

50% 

3.00 

Plant 8 Membrane Eff. 

0.3 

0.013 

4.33 

98% 

97% 

98% 

97% 

8.41 

Plant 8 Plant Eff./Measured 

2.9 







11.41 

Plant 8 Plant Eff./Predicted 

2.44 








Plant 8 Dist. Syst. 

2.82 








9/24/2001 









Plant 7 Raw 

12.7 

0.465 

3.66 

— 

— 

— 

— 


Plant 7 Settled 

10.0 

0.287 

2.86 

21% 

38% 

21% 

38% 


Plant 7 Filter Eff. 

9.3 

0.277 

2.97 

6.9% 

3.5% 

27% 

40% 


Plant 7 Ozone Eff. 

9.2 

0.224 

2.44 

1.6% 

19% 

28% 

52% 


Plant 8 Raw 

12.4 

0.454 

3.67 

— 

— 

— 

— 


Plant 8 Settled 

9.4 

0.268 

2.85 

24% 

41% 

24% 

41% 


Plant 8 Filter Eff. 

8.7 

0.257 

2.96 

7.7% 

4.1% 

30% 

43% 

3.3 

Plant 8 Membrane Eff. 

0.39 

0.012 

3.08 

97% 

97% 

97% 

97% 

6.8 

Plant 8 Plant Eff./Measured 

3.5 







10.1 

Plant 8 Plant Eff./Predicted 

3.1 








Plant 8 Dist. Syst. 

3.3 








01/14-16/2002 









Plant 7 Raw 

12.6 

0.454 

3.60 

— 

— 

— 

— 


Plant 7 Settled 

9.5 

0.262 

2.76 

25% 

42% 

25% 

42% 


Plant 7 Filter Eff. 

9.3 

0.248 

2.68 

2.2% 

5.3% 

26% 

45% 


Plant 7 Ozone Eff. 

9.2 

0.213 

2.32 

0.9% 

13% 

27% 

53% 


Plant 7 Dist. Syst. 

8.8 








Plant 8 Raw 

11.3 

0.414 

3.66 

— 

— 

— 

— 


Plant 8 Settled 

8.8 

0.248 

2.82 

22% 

40% 

22% 

40% 


Plant 8 Filter Eff. 

8.0 

0.233 

2.90 

8.6% 

6.0% 

29% 

44% 

3.0 

Plant 8 Membrane Eff. 

0.28 

0.01 

3.57 

98% 

98% 

98% 

98% 

8.6 

Plant 8 Plant Eff./Measured 

2.5 







11.6 

Plant 8 Plant Eff./Predicted 

2.3 








Plant 8 Dist. Syst. 

2.6 









a UV = Ultraviolet absorbance reported in units of "inverse centimeters" (APHA, 1998) 
b SUVA (L/mg-m) = Specific ultraviolet absorbance = 100*UV (cm'^/DOC (mg/L) or UV (m'^/DOC (mg/L), 
where DOC = dissolved organic carbon, which typically = 90-95% TOC (used TOC values in calculating SUVA) 

(e.g., UV = 0.470/cm = 0.470/(0.01 m) = 47.0/m, DOC = 12.7 mg/L, SUVA = (47.0 m' 1 )/(12.7 mg/L) = 3.70 L/mg-m) 
c (lime softening fiow)*(filter effluent TOC) + (membrane softening flow)*(membrane effluent TOC) = plant effluent TOC 


126 
































































Table 6. Miscellaneous water quality parameters at plants 7 and 8 


Location 

Bromide 

(mg/L) 

Alkalinity 

(mg/L) 

Ammonia 
(mg/L as N) 

Chlorine 
Demand 3 (mg/L) 

12/11/2000 





Plant 7 Raw 

0.12 

265 

0.73 

5.5 

Plant 8 Raw 

0.33 

249 

0.62 

4.7 

Plant 8 Membrane Eff. 

0.11 




Plant 8 Bromide Rejection (%) 

66% 




3/12/2001 





Plant 7 raw water 

0.14 

265 

0.69 

5.2 

Plant 8 raw water 

0.3 

250 

0.62 

4.7 

Plant 8 membrane effluent 

0.1 




Plant 8 bromide rejection (%) 

67% 




9/24/2001 





Plant 7 Raw 

0.14 

264 

0.62 

4.7 

Plant 8 Raw 

0.25 

236 

0.48 

3.6 

Plant 8 Membrane Eff. 

0.1 




Plant 8 Bromide Rejection (%) 

60% 




01/14-16/2002 





Plant 7 Raw 

0.14 

130 

0.67 

5.1 

Plant 8 Raw 

0.27 

236 

0.46 

3.5 

Plant 8 Membrane Eff. 

0.1 




Plant 8 Bromide Rejection (%) 

63% 





a Chlorine demand from ammonia = 7.6 x ammonia (mg/L as N) 


Biodegradable Organic Matter. Ozone can convert natural organic matter in water to 
carboxylic acids (Kuo et al., 1996) and other assimilable organic carbon (AOC) (van der Koiij et 
al., 1982). Table 7 shows the carboxylic acid and AOC data for all four sampling dates at plant 
7. In addition, Figure 3 shows the AOC results for the December 2000, March 2001, and 
September 2001 samplings. Low concentrations of AOC and certain carboxylic acids were 
detected in the raw water at plant 7. Those levels increased somewhat after chloramination and 
increased significantly after ozonation (except for the AOC in September 2001). 

Because AOC data are expressed in units of micrograms of carbon per liter (pg C/L), the 
carboxylic acid data were converted to the same units. A portion of the molecular weight (MW) 
of each carboxylic acid is due to carbon atoms (i.e., 27-49 %) and the remainder is due to oxygen 
and hydrogen atoms. The sums of the five carboxylic acids (on a pg C/L basis) were compared 
to the AOC data. On a median basis for each sample date, 23-30 % of the AOC was accounted 
for by the carboxylic acids. The amount of AOC that was accounted for by carboxylic acids in 
the ozone contactor effluent was typically greater than the percentage accounted for in the 
chloraminated water. Although carboxylic acids have been shown to be ozone by-products, they 
have not been shown to be by-products of chloramines. However, in other research (Jacangelo et 


127 



























Table 7. Formation and removal of carboxylic acids and AOC at plant 7 


Location 

Concentration 3 (pg/L) 

Concentration (pg C/L) 

Sum/ 

AOC 

Acetate 

Propionate 

Formate 

Pyruvate 

Oxalate 

Acetate 

Propionate 

Formate 

Pyruvate 

Oxalate 

Sum 

AOC 

12/11/2000 














Plant 7 Raw 

35 

ND b 

37 

NR C 

21 

14 

ND 

9.8 

NR 

5.8 

30 

111 

27% 

Plant 7 Filter Eff. 

50 

ND 

50 

NR 

54 

20 

ND 

13 

NR 

15 

48 

269 

18% 

Plant 7 Ozone Eff. 

150 

ND 

247 

NR 

324 

61 

ND 

66 

NR 

88 

215 

577 

37% 













median 

27% 

3/12/2001 














Plant 7 Raw 

ND 

ND 

23 

ND 

ND 

ND 

ND 

6.1 

ND 

ND 

6.1 

112 

5% 

Plant 7 Filter Eff. 

41 

ND 

59 

44 

60 

17 

ND 

16 

18 

16 

67 

277 

24% 

Plant 7 Ozone Eff. 

223 

ND 

369 

52 

657 

91 

ND 

98 

22 

179 

390 

1031 

38% 













median 

24% 

9/24/2001 














Plant 7 Raw 

7.1 

ND 

8.5 

ND 

5.7 

2.9 

ND 

2.3 

ND 

1.6 

6.7 

102 

7% 

Plant 7 Filter Eff. 

37 

ND 

37 

17 

35 

15 

ND 

10 

7.0 

10 

41 

197 

21% 

Plant 7 Ozone Eff. 

102 

5.2 

177 

24 

235 

41 

2.6 

47 

10 

64 

165 

203 

81% 













median 

23% 

1/14/2002 














Plant 7 Raw 

11 

ND 

73 

ND 

19 

4.6 

ND 

19 

ND 

5.1 

29 

98 

30% 

Plant 7 Filter Eff. 

28 

ND 

122 

27 

37 

11 

ND 

33 

11 

10 

65 

147 

44% 

Plant 7 Ozone Eff. 

102 

ND 

223 

40 

279 

41 

ND 

59 

16 

76 

194 

657 

29% 













median 

30% 

Formula 

CH3COO' 

CH 3 CH 2 COO' 

HCOO’ 

CHjCOCOO' 

C2O4 2 - 


MW (gm/mole) 

59 

73 

45 

87 

88 

C portion (gm/mole) 

24 

36 

12 

36 

24 

C% of MW 

41% 

49% 

27% 

41% 

27% 


a Method detection limit (MDL) = 3 (jg/L; reporting detection level (RDL) = 15 pg/L 
Values > MDL but < RDL shown in italics 
b ND = Not detected, value is < RDL 
C NR = Not reported, quality control problem 


128 












































Figure 3 


AOC Results: Plant 7 



◄—December 11, 2000-► ◄—March 12, 2001-► ◄— September 24, 2001 -► 

Sample Site 

*AOC evaluated with two test bacteria: Pseudomonas fluorescens P-17 and Spirillum NOX 


al., 1989), chloramines have been shown to be capable of producing aldehydes—other ozone by¬ 
products—at lower levels than that produced during ozonation. 

Halogenated Organic and Other Nonhalogenated Organic DBPs. Tables 8 and 9 
(12/11/00), Tables 11 and 12 (3/12/01), Tables 14 and 15 (9/24/01), and Tables 17 and 18 (1/14- 
16/02) show results for the halogenated organic DBPs that were analyzed at Metropolitan Water 
District of Southern California (MWDSC). Table 10 (12/11/00 [plant 7] and Table 16 (9/24/01 
[plant 8]) show results from broadscreen DBP analyses conducted at the U.S. Environmental 
Protection Agency (USEPA). Table 13 (3/12/01) and Table 19 (1/14-16/02) show results for 
additional target DBPs that were analyzed for at the University of North Carolina (UNC). Tables 
20-21 (1/14-16/02) show results for halogenated furanones that were analyzed at UNC. 


Summary of tables for halogenated organic and other nonhalogenated organic DBPs 


DBP Analyses (Laboratory) 

12/11/00 

3/12/01 

9/24/01 

1/14-16/02 

Halogenated organic DBPs (MWDSC) 

Tables 8-9 

Tables 11-12 

Tables 14-15 

Tables 17-18 

Additional target DBPs (UNC) 


Table 13 


Table 19 

Halogenated furanones (UNC) 




Tables 20-21 

Broadscreen analysis (USEPA) 

Table 10 a 


Table 16 b 



a Plant 7 
b Plant 8 


129 




























































Table 8. DBP results at 


2 / 11 / 00 ) 


12/11/2000 

MRL a 

Plant 7 b 

Compound 

pg/L 

Raw 

Settled 

Filt Eff 

03 Eff 

Plant Eff 

DS 

SDS 

Halomethanes 









Chloromethane 

0.15 

ND d 


ND 


ND 

ND 

ND 

Bromomethane 

0.20 

ND 


ND 


ND 

ND 

ND 

Bromochloromethane 

0.14 

ND 


ND 


ND 

ND 

ND 

Dibromomethane 

0.11 

ND 


ND 


ND 

ND 

ND 

Chloroform 6 

0.10 

ND 

10 

17 

16 

17 

16 

17 

Bromodichloromethane 6 

0.10 

ND 

1 

1 

NR f 

1 

1 

1 

Dibromochloromethane 6 

0.12 

ND 

ND 

0.1 

NR 

0.1 

0.1 

0.1 

Bromoform 6 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

0.3 

THM4 9 


ND 

11 

18 

NR 

18 

17 

18 

Dichloroiodomethane 

0.10 

ND 

ND 

ND 

ND 

0.3 

ND 

0.2 

Bromochloroiodomethane 

3 

ND 

NR 

ND 

NR 

ND 

ND 

<1 h 

Dibromoiodomethane 

0.64 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.10 

ND 

ND 

0.2 

ND 

ND 

ND 

0.2 

Bromodiiodomethane 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.14 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 

ND 


ND 


ND 

0.07 

ND 

Haloacetic acids 









Monochloroacetic acid 6 

2 


ND 

ND 


2.2 

ND 

2.6 

Monobromoacetic acid 6 

1 


1.2 

1.3 


1.6 

1.4 

1.5 

Dichloroacetic acid 6 

1 


6.5 

12 


20 

22 

27 

Bromochloroacetic acid 6 

1 


ND 

1.1 


1.7 

1.7 

2.0 

Dibromoacetic acid 6 

1 


ND 

ND 


ND 

1.0 

ND 

Trichloroacetic acid 6 

1 


1.1 

3.2 


3.4 

3.0 

3.3 

Bromodichloroacetic acid 

1 


ND 

ND 


ND 

ND 

ND 

Dibromochloroacetic acid 

1 


ND 

ND 


ND 

ND 

ND 

Tribromoacetic acid 

2 


ND 

ND 


ND 

ND 

ND 

HAA5' 



8.8 

16 


27 

27 

34 

HAA9 1 



8.8 

17 


29 

29 

36 

DXAA k 



6.5 

13 


22 

24 

29 

TXAA 1 



1.1 

3.2 


3.4 

3.0 

3.3 

Haloacetonitriles 









Chloroacetonitrile 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile 6 

0.10 

ND 

ND 

ND 

0.2 

0.3 

ND 

ND 

Bromochloroacetonitrile 6 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromoacetonitrile 6 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

T richloroacetonitrile 6 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetaldehvdes 









Dichloroacetaldehyde 

0.16 

ND 

1 

3 

12 

14 

15 

16 

Bromochloroacetaldehyde™ 

Chloral hydrate 6 

0.20 

ND 

ND 

ND 

0.3 

0.5 

0.5 

0.5 

T ribromoacetaldehyde 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


130 





























































Table 8 (continued) 


12/11/2000 

"mrl7 

Plant 7 b 

Compound 

fjg/L 

Raw 

Settled 

Filt Eff 

03 Eff 

Plant Eff 

DS 

SDS 

Haloketones 









Chloropropanone 

0.10 

ND 

ND 

0.3 

0.6 

2 

1 

2 

1,1-Dichloropropanone e 

0.10 

ND 

ND 

0.3 

0.5 

2 

ND 

ND 

1,3-Dichloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

3 

ND 


ND 


ND 

ND 

ND 

1,1,1 -T richloropropanone 6 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-T richloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

3 

ND 


ND 


ND 

ND 

ND 

1,1,1 -T ribromopropanone 

3 

ND 


ND 


ND 

ND 

ND 

1,1,3-T ribromopropanone 

3 

ND 


ND 


ND 

ND 

ND 

1,1,3,3-T etrachloropropanone 

0.10 

ND 

ND 

0.1 

ND 

ND 

ND 

ND 

1,1,3,3-T etrabromopropanone 

0.10 

ND 

0.2 

0.2 

0.1 

0.1 

ND 

ND 

Halonitromethanes 









Bromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

0.1 

Dichloronitromethane 

3 

NR 


NR 


NR 

NR 

NR 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 6 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Miscellaneous Compounds 









Methyl ethyl ketone 

1.90 

ND 


ND 


ND 

ND 

ND 

Methyl tertiary butyl ether 

0.16 

ND 


ND 


ND 

ND 

ND 

Benzyl chloride 

0.50 

ND 

NR 

ND 

NR 

ND 

ND 

ND 


a MRL = Minimum reporting level, which equals method detection limit (MDL) 
or lowest calibration standard or concentration of blank 

b Plant 7 sampled at (1) raw water, (2) settled water, (3) filter effluent (FE), (4) effluent of ozone contactor, 

(5) plant effluent (PE), (6) distribution system (DS), and (7) SDS testing of plant effluent 
c Plant 8 sampled at (1) raw water; lime softening portion of plant at (2) settled water, (3) filter effluent; 
membrane softening portion of plant at (4) effluent of stripper towers; combined treated waters at 
(5) plant effluent, (6) DS, and (7) SDS testing of plant effluent 
d ND = Not detected at or above MRL 

e DBP in the Information Collection Rule (ICR) (note: some utilities collected data for all 9 
haloacetic acids for the ICR, but monitoring for only 6 haloacetic acids was required) 
f NR = Not reported, due to interference problem on gas chromatograph or to problem with quality assurance 
9 THM4 = Sum of 4 THMs (chloroform, bromodichloromethane, dibromochloromethane, bromoform) 
h <1: Concentration less than lowest calibration standard (i.e., 1 pg/L) 

'HAA5 = Sum of 5 haloacetic acids (monochloro-, monobromo-, dichloro-, dibromo-, trichloroacetic acid) 
j HAA9 = Sum of 9 haloacetic acids 

k DXAA = Sum of dihaloacetic acids (dichloro-, bromochloro-, dibromoacetic acid) 

'TXAA = Sum of trihaloacetic acids (trichloro-, bromodichloro-, dibromochoro-, tribromoacetic acid) 
m Brornochloroacetaldehyde and chloral hydrate co-eulte; result = sum of 2 DBPs 


131 





































Table 9. DBP results at plant 8 (12/11/00) 


12/11/2000 

■mrl* 

Plant 8 C 

Compound 

pg/L 

Raw 

Settled 

Filt Eff 

Tower Eff 

Plant Eff 

DS 

SDS 

Halomethanes 









Chloromethane 

0.15 



0.2 

ND 

ND 

ND 

ND 

Bromomethane 

0.20 



ND 

ND 

ND 

ND 

ND 

Bromochloromethane 

0.14 



ND 

ND 

ND 

ND 

ND 

Dibromomethane 

0.11 



ND 

ND 

ND 

ND 

ND 

Chloroform 6 

0.10 

0.6 

15 

90 

1 

57 

61 

61 

Bromodichloromethane 6 

0.10 

ND 

NR 

22 

1 

9 

9 

9 

Dibromochloromethane 6 

0.12 

ND 

NR 

3 

0.5 

1 

1 

1 

Bromoform 6 

0.12 

ND 

ND 

0.4 

0.5 

0.8 

0.9 

0.8 

THM4 9 


0.6 

NR 

115 

3 

68 

72 

72 

Dichloroiodomethane 

0.10 

ND 

ND 

2 

0.8 

1 

1 

1 

Bromochloroiodomethane 

3 

ND 

NR 

<1 

<1 

<1 

<1 

<1 

Dibromoiodomethane 

0.64 

ND 

ND 

<1 

<1 

<1 

<1 

<1 

Chlorodiiodomethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.14 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 



ND 

ND 

ND 

ND 

ND 

Haloacetic acids 









Monochloroacetic acid 6 

2 


ND 

ND 

ND 

ND 

ND 

ND 

Monobromoacetic acid 6 

1 


1.3 

1.7 

1.3 

1.5 

1.4 

1.4 

Dichloroacetic acid 6 

1 


7.6 

35 

1.7 

21 

20 

24 

Bromochloroacetic acid 6 

1 


1.0 

6.3 

ND 

3.2 

2.7 

4.4 

Dibromoacetic acid 6 

1 


ND 

1.0 

1.1 

ND 

1.0 

1.2 

Trichloroacetic acid 6 

1 


1.8 

15 

ND 

5.8 

5.0 

6.4 

Bromodichloroacetic acid 

1 


ND 

3.2 

ND 

1.1 

1.1 

1.3 

Dibromochloroacetic acid 

1 


ND 

1.0 

ND 

ND 

ND 

ND 

Tribromoacetic acid 

2 


ND 

ND 

ND 

ND 

ND 

ND 

HAA5 1 



11 

53 

4.1 

28 

27 

33 

HAA9* 



12 

64 

4.1 

33 

31 

38 

DXAA k 



8.6 

42 

2.8 

24 

23 

29 

TXAA 1 



1.8 

19 

ND 

6.9 

6.1 

7.7 

Haloacetonitriles 









Chloroacetonitrile 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile 6 

0.10 

ND 

ND 

8 

0.2 

0.6 

0.6 

0.2 

Bromochloroacetonitrile 6 

0.10 

ND 

ND 

2 

0.2 

0.4 

0.4 

0.2 

Dibromoacetonitrile 6 

0.10 

ND 

ND 

0.2 

0.2 

0.2 

0.2 

0.1 

T richloroacetonitrile 6 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetaldehvdes 









Dichloroacetaldehyde 

0.16 

ND 

1 

3 

ND 

2 

1 

3 

Bromochioroacetaldehyde m 

Chloral hydrate 6 

0.20 

ND 

ND 

13 

0.2 

1.6 

1.5 

0.2 

T ribromoacetaldehyde 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


132 


























































Table 9 (continued) 


12/11/2000 

MRL“ 

Mg/L 

Plant 8° 

Compound 

Raw 

Settled 

Filt Eff 

Tower Eff 

Plant Eff 

DS 

SDS 

Haloketones 









Chloropropanone 

0.10 

ND 

ND 

0.3 

ND 

0.3 

0.2 

0.3 

1,1-Dichloropropanone e 

0.10 

ND 

ND 

0.4 

ND 

0.2 

0.2 

0.2 

1,3-Dichloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

3 



ND 

ND 

ND 

ND 

ND 

1,1,1 -Trichloropropanone 6 

0.10 

ND 

ND 

0.9 

0.1 

ND 

ND 

ND 

1,1,3-T richloropropanone 

0.10 

ND 

0.2 

0.2 

ND 

0.1 

0.1 

ND 

1 -Bromo-1,1 -dichloropropanone 

3 



ND 

ND 

ND 

ND 

ND 

1,1,1 -T ribromopropanone 

3 



ND 

ND 

ND 

ND 

ND 

1,1,3-T ribromopropanone 

3 



ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrabromopropanone 

0.10 

0.1 

ND 

0.1 

ND 

0.1 

ND 

0.1 

Halonitromethanes 









Bromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

3 



NR 

NR 

NR 

NR 

NR 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 6 

0.10 

ND 

ND 

0.4 

ND 

0.4 

0.4 

0.4 

Miscellaneous Compounds 









Methyl ethyl ketone 

1.90 



ND 

ND 

ND 

ND 

ND 

Methyl tertiary butyl ether 

0.16 



ND 

ND 

ND 

ND 

ND 

Benzyl chloride 

0.50 

ND 

NR 

ND 

ND 

ND 

ND 

ND 


Table 10. Occurrence of other DBPs a at plan t 7 ( 12/11/00) 


Compound 

FE 

PE 

Halomethanes 



Bromodichloromethane b 

X 

X 

Dibromochloromethane 

X 

X 

Bromoform 

X 

X 

Dichloroiodomethane 

X 

X 

Bromochloroiodomethcme 

X 

X 

Diiodochloromethcme 

X 

X 

Haloacids 



Dichloroacetic acid 

X 

X 

Bromochloroacetic acid 

X 

X 

Dibromoacetic acid 

X 

X 

Trichloroacetic acid 

X 

X 

Haloacetonitriles 



Bromochloroacetonitrile 

X 

X 

Dibromoacetonitrile 

X 

X 

Haloaldehydes 



Dibromoacetaldehyde 

- 

X 

2-Bromo-2-methylpropanal 

X 

X 

Halonitromethanes 



Dichloronitromethane 

X 

X 

Bromochloronitromethane 

- 

X 


Compound 

FE 

PE 

Haloketones 



1,1 -Dichloropropanone 

X 

X 

1 -Bromo-1 -chloropropanone 

X 

X 

1,1,1 -Trichloropropanone 

X 

X 

1,1,3-Trichloropropanone 

X 

X 

1 -Bromo-1,1 -dichloropropanone 

X 

X 

1,1,3-Tribromopropanone 

X 

X 

1,1,3,3-Tetrachloropropanone 

X 

X 

1 -Bromo-1,3,3-trichloropropanone 

X 

X 

1, l-Dibromo-3,3-dichloropropanone 

X 

X 

1,3 -Dibromo-1,3-dichloropropanone 

- 

X 

1,1,3-Tribromo-3-chloropropanone 

- 

X 

1,1,3,3-Tetrabromopropanone 

- 

X 

Pentachloropropanone 

X 

X 

Miscellaneous Halogenated DBPs 



Hexachlorocyclopentadiene 

X 

X 

Bromopentachlorocyclopentadiene 

X 

X 

Non-haloeenated DBPs 



Formaldehyde 

- 

X 

Acetone 

- 

X 

Glyoxal 

- 

X 

Methyl glyoxal 

- 

X 


a DBPs detected by broadscreen gas chromatography/mass spectrometry (GC/MS) technique 
b Compounds listed in italics were confirmed through the analysis of authentic standards; haloacids and 
non-halogenated carboxylic acids identified as their methyl esters. 


133 































































Table 11. DBP results at plant 7 (3/12/01) 


03/12/2001 

"mrl7 

Plant 7 b 

Compound 

mq/l 

Raw 

Settled 

Filt Eff 

03 Eff 

Plant Eff 

DS 

SDS 

Halomethanes 









Chloromethane 

0.15 

ND d 


ND 


ND 

ND 

ND 

Bromomethane 

0.20 

ND 


ND 


ND 

ND 

ND 

Bromochloromethane 

0.14 

ND 


ND 


ND 

ND 

ND 

Dibromomethane 

0.11 

ND 


ND 


ND 

ND 

ND 

Chloroform® 

0.1 

ND 

8 

15 

14 

13 

21 

24 

Bromodichloromethane® 

0.1 

ND 

0.8 

3 

3 

2 

3 

4 

Dibromochloromethane® 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

0.2 

Bromoform® 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

THM4 9 


ND 

9 

18 

17 

15 

24 

27 

Dichloroiodomethane 

0.25 

ND 

NR f 

ND 

NR 

ND 

ND 

ND 

Bromochloroiodomethane 

3 

ND 

NR 

ND 

NR 

ND 

ND 

ND 

Dibromoiodomethane 

0.60 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.51 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.56 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.54 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 

ND 


0.2 


0.4 

0.5 

0.4 

T ribromochloromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 









Monochloroacetic acid® 

2 


ND 

ND 


2.8 

2.6 

3.6 

Monobromoacetic acid® 

1 


ND 

ND 


ND 

ND 

ND 

Dichloroacetic acid® 

1 


7.4 

12 


22 

20 

32 

Bromochloroacetic acid® 

1 


ND 

1.0 


1.7 

1.5 

2.1 

Dibromoacetic acid® 

1 


ND 

ND 


ND 

ND 

ND 

Trichloroacetic acid® 

1 


1.2 

4.0 


5.1 

3.5 

5.6 

Bromodichloroacetic acid 

1 


ND 

ND 


ND 

ND 

ND 

Dibromochloroacetic acid 

1 


ND 

ND 


ND 

ND 

ND 

Tribromoacetic acid 

2 


ND 

ND 


ND 

ND 

ND 

HAA5' 



8.6 

16 


30 

26 

41 

HAA9 J 



8.6 

17 


32 

28 

43 

DXAA k 



7.4 

13 


24 

22 

34 

TXAA' 



1.2 

4.0 


5.1 

3.5 

5.6 

Haloacetonitriles 









Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile® 

0.10 

ND 

ND 

0.2 

0.2 

0.5 

0.2 

0.3 

Bromochloroacetonitrile® 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromoacetonitrile® 

0.17 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

T richloroacetonitrile® 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetaldehydes 









Dichloroacetaldehyde 

0.16 

ND 

0.8 

3 

6 

9 

9 

10 

Bromochloroacetaldehyde 

0.1 

ND 

ND 

0.2 

ND 

0.1 

ND 

ND 

Chloral hydrate® 

0.1 

ND 

ND 

0.1 

ND 

0.7 

0.5 

0.6 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


134 
































































Table 11 (continued) 


03/12/2001 

Imrl 7 

pg/L 

Plant 7 b 

Compound 

Raw 

Settled 

Filt Eff 

03 Eff 

Plant Eff 

DS 

SDS 

Haloketones 









Chloropropanone 

0.5 

ND 

ND 

ND 

ND 

0.7 

ND 

ND 

1,1-Dichloropropanone e 

0.11 

ND 

ND 

0.2 

0.5 

1 

0.5 

0.8 

1,3-Dichloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

3 

ND 


ND 


ND 

ND 

ND 

1,3-Dibromopropanone 

3 

ND 


ND 


ND 

ND 

ND 

1,1,1-Trichloropropanone e 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-T richloropropanone 

0.11 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

3 

ND 


ND 


ND 

ND 

ND 

1,1,1 -T ribromopropanone 

3 

ND 


ND 


ND 

ND 

ND 

1,1,3-T ribromopropanone 

3 

ND 


ND 


ND 

ND 

ND 

1,1,3,3-Tetrachloropropanone 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-Tetrachloropropanone 

3 

ND 


ND 


ND 

ND 

ND 

1,1,3,3-Tetrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 









Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

3 

ND 


ND 


ND 

ND 

ND 

Bromochloronitromethane 

3 

ND 


ND 


ND 

ND 

ND 

Dibromonitromethane 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Miscellaneous Compounds 









Methyl ethyl ketone 

1.90 

ND 


ND 


ND 

ND 

ND 

Methyl tertiary butyl ether 

0.16 

ND 


ND 


ND 

ND 

ND 

Benzyl chloride 

2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


135 







































Table 12. DBP results at plant 8 (3/12/01) 


03/12/2001 

MRL d 

Plant 8 C 

Compound 

|jg/L 

Raw 

Settled 

Filt Eff 

Tower Eff 

Plant Eff 

DS 

SDS 

Halomethanes 









Chloromethane 

0.15 



ND 

ND 

ND 

ND 

ND 

Bromomethane 

0.20 



ND 

ND 

ND 

ND 

ND 

Bromochloromethane 

0.14 



ND 

ND 

ND 

ND 

ND 

Dibromomethane 

0.11 



ND 

ND 

ND 

ND 

ND 

Chloroform 6 

0.1 

ND 

14 

81 

1 

41 

42 

42 

Bromodichloromethane 6 

0.1 

ND 

3 

15 

0.6 

7 

7 

7 

Dibromochloromethane 6 

0.10 

ND 

0.2 

2 

0.2 

2 

2 

2 

Bromoform 6 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

THM4 9 


ND 

17 

98 

2 

50 

51 

50 

Dichloroiodomethane 

0.25 

NR 

NR 

2 

ND 

0.7 

0.6 

0.7 

Bromochloroiodomethane 

3 

NR 

NR 

<1 h 

ND 

<1 

<1 

<1 

Dibromoiodomethane 

0.60 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.51 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.56 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.54 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 



0.7 

ND 

0.5 

0.5 

0.4 

T ribromochloromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 









Monochloroacetic acid 6 

2 


ND 

ND 

2.4 

ND 

2.2 

ND 

Monobromoacetic acid 6 

1 


ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetic acid 6 

1 


6.3 

36 

1.0 

14 

14 

15 

Bromochloroacetic acid 6 

1 


1.0 

3.8 

ND 

2.0 

2.2 

2.3 

Dibromoacetic acid 6 

1 


ND 

ND 

ND 

ND 

ND 

ND 

Trichloroacetic acid 6 

1 


1.3 

9.1 

ND 

2.5 

2.4 

2.5 

Bromodichloroacetic acid 

1 


ND 

1.6 

ND 

ND 

ND 

ND 

Dibromochloroacetic acid 

1 


ND 

ND 

ND 

ND 

ND 

ND 

Tribromoacetic acid 

2 


ND 

ND 

ND 

ND 

ND 

ND 

HAA5' 



7.6 

45 

3.4 

17 

19 

18 

HAA9* 



8.6 

51 

3.4 

19 

21 

20 

DXAA k 



7.3 

40 

1.0 

16 

16 

17 

txaa' 



1.3 

11 

ND 

2.5 

2.4 

2.5 

Haloacetonitriles 









Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile 6 

0.10 

ND 

ND 

3 

0.1 

0.5 

0.5 

0.2 

Bromochloroacetonitrile 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromoacetonitrile 6 

0.17 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

T richloroacetonitrile 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetaldehydes 









Dichloroacetaldehyde 

0.16 

0.2 

0.3 

0.8 

ND 

0.7 

0.7 

1 

Bromochloroacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloral hydrate 6 

0.1 

ND 

ND 

5.7 

0.5 

0.4 

0.4 

0.3 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


136 






























































Table 12 (continued) 


03/12/2001 

MRL d 

Plant 8 C 

Compound 

mq/l 

Raw 

Settled 

Filt Eff 

Tower Eff 

Plant Eff 

DS 

SDS 

Haloketones 









Chloropropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dichloropropanone e 

0.11 

ND 

ND 

0.3 

ND 

0.1 

0.1 

0.1 

1,3-Dichloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

3 



ND 

ND 

ND 

ND 

ND 

1,3-Dibromopropanone 

3 



ND 

ND 

ND 

ND 

ND 

1,1,1 -T richloropropanone 6 

0.10 

ND 

ND 

0.2 

ND 

ND 

ND 

ND 

1,1,3-T richloropropanone 

0.11 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

3 



ND 

ND 

ND 

ND 

ND 

1,1,1 -T ribromopropanone 

3 



ND 

ND 

ND 

ND 

ND 

1,1,3-T ribromopropanone 

3 



ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrachloropropanone 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-Tetrachloropropanone 

3 



ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 









Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

0.3 

0.3 

0.1 

Dichloronitromethane 

3 



ND 

ND 

ND 

ND 

ND 

Bromochloronitromethane 

3 



ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 6 

0.1 

ND 

ND 

0.2 

ND 

0.1 

0.1 

0.2 

Miscellaneous Compounds 









Methyl ethyl ketone 

1.90 



ND 

ND 

ND 

ND 

ND 

Methyl tertiary butyl ether 

0.16 



0.9 

ND 

ND 

ND 

ND 

Benzyl chloride 

2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


137 








































Table 13. Additional target DBP results (pg/L) at plants 7 and 8 (3/12/01) 


3/12/01 

Plant T 

Plant 8 a 

Compound 

Raw 

FE 

OE 

PE 

DS 

SDS 

Raw 

FE 

STE 

PE 

DS 

SDS 

Monochloroacetaldehyde 

0 

0.2 

1.2 

0.7 

0.5 

0.5 

0 

0 

0 

0 

0 

0 

Dichloroacetaldehyde 

0 

2.4 

4.4 

6.8 

7.6 

8.6 

0.1 

0.7 

0 

0.5 

0.6 

0.6 

Bromochloroacetaldehyde 













3,3-Dichloropropenoic acid 

0.6 




0.4 


0 




0 


Bromochloromethylacetate 

0 




0 


0 




0 


2,2-Dichloroacetamide 

0 

0.2 

0.1 

1.8 

2.5 

3.0 

0 

4.0 

0 

2.1 

2.2 

3.4 

TOX (pg/L as Cl') 

24.2 

205 

127 

203 

121 

207 

33.0 

459 

41 

142 

157 

130 

Cyanoformaldehyde 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

5-Keto-l-hexanal 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

6-Hydroxy-2-hexanone 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

Dimethylglyoxal 

0.4 

0.2 

4.0 

3.5 

1.4 

1.9 

0.3 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

//-<my-2-Hexenal 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 


a Plant 7 or plant 8 sampled at (1) raw water, (2) filter effluent (FE), (3) ozone contactor effluent (OE) or stripper tower 
effluent (STE), (4) finished water at plant effluent (PE), (5) distribution system (DS) at average detention time, and 
(6) SDS sample. 


138 






























Table 14. DBP results 


09/24/2001 

■mrlT 

Plant 7 b 

Compound 

mq/l 

Raw 

Settled 

Filt Eff 

03 Eff 

Plant Eff 

DS 

SDS 

Halomethanes 









Chloromethane 

0.2 

ND d 


ND 


ND 

0.2 

ND 

Bromomethane 

0.2 

ND 


ND 


ND 

ND 

ND 

Bromochloromethane 

0.5 

ND 


ND 


ND 

ND 

ND 

Dibromomethane 

0.5 

ND 


ND 


ND 

ND 

ND 

Chloroform 6 

0.1 

ND 

3 

3 

3 

7 

11 

12 

Bromodichloromethane 6 

0.1 

ND 

0.3 

0.3 

0.4 

1 

1 

1 

Dibromochloromethane 6 

0.1 

ND 

ND 

ND 

ND 

0.1 

0.1 

0.2 

Bromoform 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

THM4 9 


ND 

3 

3 

3 

8 

12 

13 

Dichloroiodomethane 

0.5 

ND 

NR f 

ND 

NR 

ND 

0.6 

0.6 

Bromochloroiodomethane 

0.25 

ND 

NR 

ND 

NR 

ND 

ND 

ND 

Dibromoiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 

ND 


ND 


ND 

ND 

ND 

T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 









Monochloroacetic acid 6 

2 


ND 

ND 


4.2 

3.7 

4.4 

Monobromoacetic acid 6 

1 


ND 

ND 


ND 

ND 

ND 

Dichloroacetic acid 6 

1 


4.7 

4.2 


16 

16 

20 

Bromochloroacetic acid 6 

1 


ND 

ND 


1.9 

1.6 

1.8 

Dibromoacetic acid 6 

1 


ND 

ND 


ND 

ND 

ND 

Trichloroacetic acid 6 

1 


1.1 

1.1 


2.0 

2.5 

2.3 

Bromodichloroacetic acid 

1 


ND 

ND 


ND 

ND 

ND 

Dibromochloroacetic acid 

1 


ND 

ND 


ND 

ND 

ND 

Tribromoacetic acid 

2 


ND 

ND 


ND 

ND 

ND 

HAA5 1 



5.8 

5.3 


22 

22 

27 

HAA9* 



5.8 

5.3 


24 

24 

29 

DXAA k 



4.7 

4.2 


18 

18 

22 

TXAA' 



1.1 

1.1 


2.0 

2.5 

2.3 

Haloacetonitriles 









Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile 6 

0.1 

ND 

0.3 

0.1 

0.2 

0.6 

0.6 

0.3 

Bromochloroacetonitrile 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromoacetonitrile 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

T richloroacetonitrile 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 


ND 

ND 

ND 



Dibromochloroacetonitrile 

0.5 

ND 


ND 

ND 

ND 



T ribromoacetonitrile 

0.90 

ND 


ND 

ND 

ND 



Haloacetaldehydes 









Dichloroacetaldehyde 

0.22 

ND 

0.9 

1 

2 

14 

14 

15 

Bromochloroacetaldehyde 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloral hydrate 6 

0.1 

0.6 

0.6 

0.6 

0.4 

0.6 

0.4 

0.3 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


139 
































































Table 14 (continued) 


09/24/2001 

MRL* 

Plant 7 b 

Compound 

mq/l 

Raw 

Settled 

Filt Eff 

03 Eff 

Plant Eff 

DS 

SDS 

Haloketones 









Chloropropanone 

0.1 

ND 

0.1 

0.1 

0.4 

0.8 

0.8 

0.8 

1,1-Dichloropropanone 6 

0.10 

ND 

0.3 

0.2 

0.2 

1 

1 

0.5 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T richloropropanone® 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

0.4 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-T ribromopropanone 

0.5 

ND 

ND 

0.6 

ND 

ND 

ND 

ND 

1,1,3,3-T etrachloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-T etrachloropropanone 

0.10 

ND 

ND 

0.4 

0.1 

ND 

ND 

ND 

1,1,3,3-Tetrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 









Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

ND 

ND 

ND 

ND 

0.3 

0.2 

0.3 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin® 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloronitromethane 

0.5 

ND 


ND 

ND 

1 



Dibromochloronitromethane 

0.5 

ND 


ND 

ND 

0.8 



Bromopicrin 

0.5 

ND 


ND 

ND 

ND 



Miscellaneous Compounds 









Methyl ethyl ketone 

0.5 

ND 


ND 


1 

ND 

0.9 

Methyl tertiary butyl ether 

0.2 

ND 


ND 


ND 

ND 

ND 

Benzyl chloride 

0.25 

ND 

NR 

ND 

NR 

ND 

ND 

ND 

1,1,2,2-Tetrabromo-2-chloroethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


140 











































Table 15. DBP results at plant 8 (9/24/01) 


09/24/2001 

MRL“ 

Plant 8 C 

Compound 

pg/L 

Raw 

Settled 

Filt Eff 

Tower Eff 

Plant Eff 

DS 

SDS 

Halomethanes 









Chloromethane 

0.2 



ND 

ND 

ND 

ND 

ND 

Bromomethane 

0.2 



ND 

ND 

ND 

ND 

ND 

Bromochloromethane 

0.5 



ND 

ND 

ND 

ND 

ND 

Dibromomethane 

0.5 



ND 

ND 

ND 

ND 

ND 

Chloroform® 

0.1 

1 

16 

63 

0.5 

35 

27 

26 

Bromodichloromethane® 

0.1 

0.2 

2 

10 

0.4 

5 

5 

5 

Dibromochloromethane® 

0.1 

ND 

0.2 

1 

0.2 

0.9 

1 

1 

Bromoform® 

0.1 

ND 

ND 

ND 

ND 

0.1 

0.2 

0.2 

THM4 9 


1 

18 

74 

1 

41 

33 

32 

Dichloroiodomethane 

0.5 

NR 

NR 

7 

ND 

3 

2 

4 

Bromochloroiodomethane 

0.25 

NR 

NR 

ND 

ND 

ND 

0.3 

0.3 

Dibromoiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 



ND 

ND 

ND 

ND 

ND 

T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 









Monochloroacetic acid® 

2 


ND 

4.1 

ND 

2.4 

ND 

2.3 

Monobromoacetic acid® 

1 


ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetic acid® 

1 


7.0 

28 

1.5 

18 

19 

19 

Bromochloroacetic acid® 

1 


ND 

3.0 

ND 

2.5 

2.6 

3.4 

Dibromoacetic acid® 

1 


ND 

ND 

ND 

ND 

1.0 

1.0 

Trichloroacetic acid® 

1 


2.0 

7.3 

ND 

3.2 

3.3 

3.0 

Bromodichloroacetic acid 

1 


ND 

1.6 

ND 

ND 

ND 

ND 

Dibromochloroacetic acid 

1 


ND 

ND 

ND 

ND 

ND 

ND 

Tribromoacetic acid 

2 


ND 

ND 

ND 

ND 

ND 

ND 

HAA5' 



9.0 

39 

1.5 

24 

23 

25 

HAA9 j 



9.0 

44 

1.5 

26 

26 

29 

DXAA k 



7.0 

31 

1.5 

21 

23 

23 

TXAA 1 



2.0 

8.9 

ND 

3.2 

3.3 

3.0 

Haloacetonitriles 









Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

0.1 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile® 

0.1 

ND 

ND 

2 

0.2 

0.5 

0.8 

0.3 

Bromochloroacetonitrile® 

0.1 

ND 

ND 

0.3 

0.1 

0.4 

0.6 

0.3 

Dibromoacetonitrile® 

0.1 

ND 

ND 

ND 

ND 

0.2 

0.2 

0.1 

T richloroacetonitrile® 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 


ND 

ND 

ND 

ND 



Dibromochloroacetonitrile 

0.5 


ND 

ND 

ND 

ND 



T ribromoacetonitrile 

0.90 


ND 

ND 

ND 

ND 



Haloanataldehydes 









Dichloroacetaldehyde 

0.22 

0.2 

4 

2 

ND 

0.9 

2 

2 

Bromochloroacetaldehyde 

0.5 

ND 

0.6 

ND 

ND 

ND 

ND 

ND 

Chloral hydrate® 

0.1 

0.7 

0.9 

3 

0.2 

0.3 

0.7 

0.3 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


141 
































































Table 15 (continued) 


09/24/2001 

"mrl7 

M9/L 

Plant 8 C 

Compound 

Raw 

Settled 

Filt Eff 

Tower Eff 

Plant Eff 

DS 

SDS 

Haloketones 









Chloropropanone 

0.1 

ND 

0.1 

0.2 

0.5 

0.1 

0.2 

0.4 

1,1 -Dichloropropanone 6 

0.10 

ND 

ND 

0.5 

0.1 

0.3 

0.3 

0.2 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T richloropropanone 6 

0.1 

ND 

ND 

0.2 

ND 

0.1 

ND 

ND 

1,1,3-Trichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-T ribromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrachloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-T etrachloropropanone 

0.10 

ND 

0.5 

0.2 

ND 

ND 

ND 

ND 

1,1,3,3-T etrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 









Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin® 

0.1 

ND 

ND 

0.2 

ND 

ND 

0.1 

0.2 

Bromodichloronitromethane 

0.5 


ND 

0.5 

ND 

0.5 



Dibromochloronitromethane 

0.5 


ND 

ND 

ND 

0.6 



Bromopicrin 

0.5 


ND 

ND 

0.6 

0.6 



Miscellaneous Compounds 









Methyl ethyl ketone 

0.5 



ND 

ND 

ND 

ND 

0.9 

Methyl tertiary butyl ether 

0.2 



ND 

ND 

ND 

ND 

ND 

Benzyl chloride 

0.25 

NR 

NR 

ND 

ND 

ND 

ND 

ND 

1,1,2,2-T etrabromo-2-chloroethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


142 











































8 


a DBPs detected by broadscreen gas chromatography/mass spectrometry (GC/MS) technique 
b Compounds listed in italics were confirmed through the analysis of authentic standards; haloacids and 
non-halogenated carboxylic acids identified as their methyl esters. 


( 9/24/01) 


Compound 

Miscellaneous Halogenated DBPs 

FE 

PE 

Hexachlorocyclopentadiene 

Bromopentachlorocyclopentadiene 

X 

X 

X 

X 

Non-halogenated DBPs 

Acetone 

X 

X 

Propanal 

X 

X 

2-Butanone 

X 

X 

3-Hexanone 

X 

X 

2-Hexanone 

X 

X 

Glyoxal 

X 

X 

Methyl glyoxal 

X 

X 

Heptanoic acid 

- 

X 

Octanoic acid 

- 

X 

Nonanoic acid 

- 

X 

Decanoic acid 

- 

X 

Undecanoic acid 

- 

X 

Dodecanoic acid 

- 

X 

Tetradecanoic acid 

- 

X 

Pentadecanoic acid 

- 

X 

Hexadecanoic acid 

- 

X 

Heptadecanoic acid 

- 

X 

Octadecanoic acid 

- 

X 

Butanedioic acid 

- 

X 

Pentanedioic acid 

- 

X 

Octanedioic acid 

- 

X 

Nonanedioic acid 

- 

X 

Decanedioic acid 

- 

X 

Benzene-1,3-dicarboxylic acid 

- 

X 


Table 16. Occurrence of other DBPs 3 at plan t 


Compound 

Halomethanes 

Dibromomethane 

Bromodichloromethane b 

Dibromochloromethane 

Bromoform 

Dichloroiodomethane 

Bromochloroiodomethane 

Diiodochloromethane 

FE 

X 

X 

X 

X 

X 

X 

X 

PE 

X 

X 

X 

X 

X 

X 

X 

Haloacids 

Bromoacetic acid 

X 


Dichloroacetic acid 

X 

X 

Bromochloroacetic acid 

X 

X 

Dibromoacetic acid 

X 

X 

Bromodichloroacetic acid 

X 

X 

Trichloroacetic acid 

X 

X 

Haloacetonitriles 

Dichloroacetonitrile 

X 

X 

Bromochloroacetonitrile 

X 

X 

Dibromoacetonitrile 

X 

X 

Haloaldehvdes 

Dichloroacetaldehyde 

X 

X 

Dibromoacetaldehyde 

- 

X 

Trichloroacetaldehyde 

- 

X 

2-Bromo-2-methylpropanal 

X 

X 

Haloketones 

Chloropropanone 

X 

X 

1,1 -Dichloropropanone 

X 

X 

1 -Bromo-1 -chloropropanone 

X 

X 

1,1,3-Trichloropropanone 

- 

X 

1 -Bromo-1,1 -dichloropropanone 

- 

X 

1,1,3,3-Tetrachloropropanone 

X 

X 

1 -Bromo-1,3,3-trichloropropanone 

X 

X 

1,1 -Dibromo-3,3-dichloropropanone 

X 

X 

1,3-Dibromo-1,3-dichloropropanone 

X 

X 

1,1,3- Tribromo-3-chloropropanone 

X 

X 

1,1,3,3-Tetrabromopropanone 

X 

X 

Halonitromethanes 

Dichloronitromethane 

X 

X 

Bromochloronitromethane 

- 

X 


143 























Table 17. DBP results at plant 7 (1/14/02) 


1/14/2002 

MRL a 

yg/L 

Plant 7 b 

Compound 

Raw 

Settled 

Filt Eff 

03 Eff 

Plant Eff 

DS 

SDS 

Halomethanes 









Chloromethane 

0.2 

ND d 


ND 


ND 

ND 

ND 

Bromomethane 

0.2 

ND 


ND 


ND 

ND 

ND 

Bromochloromethane 

0.5 

ND 


ND 


ND 

ND 

ND 

Dibromomethane 

0.5 

ND 


ND 


ND 

ND 

ND 

Chloroform® 

0.2 

ND 

NR f 

3 

4 

6 

8 

8 

Bromodichloromethane® 

0.2 

ND 

NR 

0.3 

0.6 

2 

1 

1 

Dibromochloromethane® 

0.5 

ND 

ND 

0.5 

<0.5" 

<0.5 

ND 

ND 

Bromoform® 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

THM4 9 


ND 

NR 

4 

5 

8 

9 

9 

Dichloroiodomethane 

2.5 

ND 

NR 

ND 

NR 

ND 

ND 

ND 

Bromochloroiodomethane 

0.5 

ND 

NR 

ND 

ND 

ND 

ND 

ND 

Dibromoiodomethane 

0.53 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.22 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 

ND 


ND 

ND 

ND 

0.2 

ND 

T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 









Monochloroacetic acid® 

2 


ND 

ND 


3.7 

4.1 

5.4 

Monobromoacetic acid® 

1 


ND 

ND 


ND 

ND 

ND 

Dichloroacetic acid® 

1 


ND 

3.9 


15 

15 

22 

Bromochloroacetic acid® 

1 


ND 

ND 


1.6 

1.6 

2.0 

Dibromoacetic acid® 

1 


ND 

ND 


ND 

ND 

ND 

Trichloroacetic acid® 

1 


ND 

ND 


1.8 

1.7 

2.0 

Bromodichloroacetic acid 

1 


ND 

ND 


ND 

ND 

ND 

Dibromochloroacetic acid 

1 


ND 

ND 


ND 

ND 

ND 

Tribromoacetic acid 

2 


ND 

ND 


ND 

ND 

ND 

HAA5' 



ND 

3.9 


21 

21 

29 

HAA9* 



ND 

3.9 


22 

22 

31 

DXAA k 



ND 

3.9 


17 

17 

24 

TXAA 1 



ND 

ND 


1.8 

1.7 

2.0 

Haloacetonitriles 









Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile® 

NA 

ND 

ND 

ND 

ND 

0.6 

NR 

NR 

Bromochloroacetonitrile® 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromoacetonitrile® 

0.25 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

T richloroacetonitrile® 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

NA 

ND 


ND 

ND 

ND 



Dibromochloroacetonitrile 

NA 

ND 


ND 

ND 

ND 



T ribromoacetonitrile 

NA 

ND 


ND 

ND 

ND 



Haloacetaldehydes 









Dichloroacetaldehyde 

0.98 

ND 

ND 

ND 

ND 

8 

9 

11 

Bromochloroacetaldehyde 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloral hydrate® 

0.1 

0.7 

0.2 

ND 

0.1 

0.5 

0.3 

0.7 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


n <0.5: Concentration less than MRL of 0.5 pg/L 


144 































































Table 17 (continued) 


1/14/2002 

"mrl* 

Plant 7 b 

Compound 

Mg/L 

Raw 

Settled 

Filt Eff 

03 Eff 

Plant Eff 

DS 

SDS 

Haloketones 









Chloropropanone 

0.5 

ND 

NR 

ND 

NR 

1 

1 

ND 

1,1-Dichloropropanone e 

NA 

ND 

ND 

ND 

ND 

1 

NR 

NR 

1,3-Dichloropropanone 

0.1 

0.2 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T richloropropanone 6 

0.1 

ND 

ND 

ND 

ND 

0.1 

ND 

ND 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-T etrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 









Chloronitromethane 

0.5 

ND 


0.6 

0.6 

0.5 

ND 

ND 

Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

NA 

ND 

NR 

0.4 

0.5 

0.7 

NR 

NR 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 6 

0.1 

ND 

ND 

ND 

0.1 

0.4 

0.2 

0.4 

Bromodichloronitromethane 

NA 

ND 


ND 

ND 

3 



Dibromochloronitromethane 

NA 

ND 


ND 

ND 

ND 



Bromopicrin 

NA 

ND 


ND 

ND 

ND 



Miscellaneous Compounds 









Methyl ethyl ketone 

0.5 

ND 


ND 


0.6 

0.8 

0.9 

Methyl tertiary butyl ether 

0.2 

ND 


ND 


ND 

ND 

ND 

Benzyl chloride 

0.2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,2,2-T etrabromo-2-chloroethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


145 












































Table 18. DBP results at plant 8 (1/16/02) 


1/16/2002 

MRL d 

pg/L 

Plant 8 C 

Compound 

Raw 

Settled 

Filt Eff 

Tower Eff 

Plant Eff 

DS 

SDS 

Halomethanes 









Chloromethane 

0.2 



ND d 

ND 

ND 

ND 

ND 

Bromomethane 

0.2 



ND 

ND 

ND 

ND 

ND 

Bromochloromethane 

0.5 



ND 

ND 

ND 

ND 

ND 

Dibromomethane 

0.5 



ND 

ND 

ND 

ND 

ND 

Chloroform 6 

0.2 

ND 

14 

59 

0.3 

25 

32 

28 

Bromodichloromethane 6 

0.2 

ND 

2 

6 

0.9 

3 

3 

3 

Dibromochloromethane 6 

0.5 

ND 

0.8 

0.9 

0.8 

0.7 

0.7 

0.5 

Bromoform 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

THM4 9 


ND 

17 

66 

2 

29 

36 

32 

Dichloroiodomethane 

2.5 

NR f 

NR 

3 

ND 

<2.5° 

<2.5 

ND 

Bromochloroiodomethane 

0.5 

NR 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromoiodomethane 

0.53 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.22 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 


0.2 

0.3 

0.6 

ND 

ND 

ND 

T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 









Monochloroacetic acid 6 

2 


ND 

2.7 

3.4 

ND 

ND 

2.7 

Monobromoacetic acid 6 

1 


ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetic acid 6 

1 


9.9 

28 

1.2 

17 

16 

16 

Bromochloroacetic acid 6 

1 


ND 

2.6 

ND 

1.5 

1.4 

1.9 

Dibromoacetic acid 6 

1 


ND 

ND 

ND 

ND 

ND 

ND 

Trichloroacetic acid 6 

1 


2.1 

6.8 

ND 

2.6 

2.4 

2.4 

Bromodichloroacetic acid 

1 


ND 

1.3 

ND 

ND 

ND 

2.5 

Dibromochloroacetic acid 

1 


ND 

ND 

ND 

ND 

ND 

ND 

Tribromoacetic acid 

2 


ND 

ND 

ND 

ND 

ND 

ND 

HAA5' 



12 

38 

4.6 

20 

18 

21 

HAA9* 



12 

41 

4.6 

21 

20 

26 

DXAA k 



10 

31 

1.2 

19 

17 

18 

TXAA' 



2.1 

8.1 

ND 

2.6 

2.4 

4.9 

Haloaceionitriles 









Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile 6 

NA 

ND 

ND 

0.9 

ND 

ND 

NR 

NR 

Bromochloroacetonitrile 6 

0.5 

ND 

ND 

<0.5 n 

ND 

<0.5 

<0.5 

<0.5 

Dibromoacetonitrile 6 

0.25 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

T richloroacetonitrile 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

NA 


ND 

ND 

ND 

ND 



Dibromochloroacetonitrile 

NA 


ND 

ND 

ND 

ND 



Tribromoacetonitrile 

NA 


ND 

ND 

ND 

ND 



Haloacetaldehydes 









Dichloroacetaldehyde 

0.98 

1 

ND 

1 

ND 

ND 

ND 

1 

Bromochloroacetaldehyde 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloral hydrate 6 

0.1 

0.3 

0.7 

2 

0.3 

0.2 

0.2 

0.1 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


°<2.5: Concentration less than MRL of 2.5 pg/L 


146 
































































Table 18 (continued) 


1/16/2002 

MRL* 

mq/l 

Plant 8 C 

Compound 

Raw 

Settled 

Filt Eff 

Tower Eff 

Plant Eff 

DS 

SDS 

Haloketones 









Chloropropanone 

0.5 

ND 

NR 

ND 

ND 

ND 

ND 

ND 

1,1 -Dichloropropanone® 

NA 

ND 

ND 

0.9 

ND 

ND 

NR 

NR 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T richloropropanone 8 

0.1 

ND 

ND 

0.5 

ND 

ND 

ND 

ND 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-T etrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 









Chloronitromethane 

0.5 


2 

<0.5 

<0.5 

ND 

ND 

ND 

Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

NA 

ND 

0.4 

0.5 

ND 

ND 

NR 

NR 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 8 

0.1 

ND 

ND 

0.6 

ND 

0.4 

0.3 

0.3 

Bromodichloronitromethane 

NA 


ND 

1 

1 

0.9 



Dibromochloronitromethane 

NA 


ND 

ND 

ND 

ND 



Bromopicrin 

NA 


ND 

ND 

1 

ND 



Miscellaneous Compounds 









Methyl ethyl ketone 

0.5 



ND 

1 

ND 

<0.5 

ND 

Methyl tertiary butyl ether 

0.2 



ND 

0.3 

ND 

ND 

ND 

Benzyl chloride 

0.2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,2,2-T etrabromo-2-chloroethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


147 












































Table 19. Additional target DBP results (pg/L) at plants 7 and 8 (1/14-16/02) 


1/14-16/02 

Plant T 

Plant 8 a 

Compound 

Raw 

FE 

OE 

PE 

DS 

SDS 

Raw 

FE 

STE 

PE 

DS 

SDS 

Monochloroacetaldehyde 

0 

0 

3.1 

1.9 

1.5 

2.2 

0 

0.2 

0 


0 

0 

Dichloroacetaldehyde 

0 

1.6 

7.5 

12.2 

9.2 

13.1 

0 

1.3 

0 


0.9 

1.0 

Bromochloroacetaldehyde 

0 

0.1 

0.2 

0.6 

0.4 

0.6 

0 

0.3 

0 


0.1 

0.1 

3,3-Dichloropropenoic acid 

0 

0 

0 

0 

0 

0.6 

0 

0.1 

0 

0 

0 

0 

Bromochloromethylacetate 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

Monochloroacetamide 

0 

0 

0 

0 

0 

0 

0 



0 

0 

0 

Monobromoacetamide 

0 

0 

0 

0 

0 

0 

0 



0 

0 

0 

Dichloroacetamide 

0 

0.1 

0.2 

1.8 

2.5 

3.0 

0 



1.5 

1.4 

1.2 

Dibromoacetamide 

0 

0 

0 

0.2 

0.4 

0.5 

0 



0.3 

0.2 

0.2 

T richloroacetamide 

0 

0 

0 

0.1 

0.2 

0.3 

0 



0.1 

0.6 

0.5 

TOX (pg/L as Cl ) 

0 

94.9 

94.2 

200 

154 

212 

0 

486 

40.4 

179 

161 

133 

TOBr (pg/L as Br ) 


17.0 

12.0 

36.5 

23.2 

42.1 

0 

137 

24.0 

80.9 

64.0 

68.0 

TOC1 (pg/L as Cl ) 


83.5 

85.0 

206 

121 

185 

0 

450 

29.7 

203 

189 

190 

Cyanoformaldehyde 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

5-Keto-l-hexanal 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

6-Hydroxy-2-hexanone 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

Dimethylglyoxal 

<0.1 

<0.1 

2.4 

2.8 

1.9 

2.5 

<0.1 

0.8 

<0.1 

<0.1 

<0.1 

<0.1 

/nms-2-Hexenal 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 


148 



































Table 20. Halogenated furanone resu 


ts (ng/L) at plant 7 (1/14/02) 


Compound 

Raw 

FE 

OE 

PE 

DS 

SDS 

BMX-1 

<0.02 

<0.02 

<0.02 

0.03 

<0.02 

0.02 

BEMX-1 

<0.02 

<0.02 

0.03 

<0.02 

<0.02 

<0.02 

BMX-2 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

BEMX-2 

<0.02 

<0.02 

<0.02 

0.06 

0.06 

0.03 

BMX-3 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

BEMX-3 

0.10 

0.10 

0.15 

0.28 

0.18 

0.18 

MX 

<0.02 

<0.02 

<0.02 

0.17 

<0.02 

0.04 

EMX 

<0.02 

<0.02 

<0.02 

0.05 

<0.02 

<0.02 

ZMX 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

(0.013) 

Ox-MX 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

Mucochloric acid {ring) 

<0.02 

<0.02 

<0.02 

(0.015) 

0.02 

0.05 

0.02 

Mucochloric acid {open) 

<0.02 

0.03 

0.08 

0.20 

0.21 

0.22 


Table 21. Halogenated furanone results (ng/L) at plant 8 (1/16/02) 


Compound 

Raw 

FE 

PE 

DS 

SDS 

BMX-1 

<0.02 

<0.02 

0.11 

0.03 

0.05 

BEMX-1 

0.08 

<0.02 (0.011) 

0.72 

<0.02 

<0.02 

BMX-2 

<0.02 

<0.02 

<0.02 (0.014) 

0.03 

0.02 

BEMX-2 

<0.02 

0.12 

0.81 

0.11 

0.10 

BMX-3 

<0.02 

<0.02 

0.04 

<0.02 

<0.02 

BEMX-3 

<0.02 

0.43 

0.41 

0.37 

1.28 

MX 

<0.02 

<0.02 (0.015) 

0.10 

0.12 

0.10 

EMX 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

ZMX 

<0.02 

0.09 

<0.02 

<0.02 

<0.02 

Ox-MX 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

Mucochloric acid {ring) 

<0.02 

0.02 

0.02 

0.02 

0.02 

Mucochloric acid {open) 

<0.02 

0.30 

0.16 

0.17 

0.18 


149 










































Halomethanes. Pre-chloramination at plant 7 resulted in the formation of 3-18 pg/L of 
the four regulated trihalomethanes (THM4) by the filter effluent sampling point. Post-ozonation 
did not change the concentration of the THMs. Post-chlorination at plant 7 resulted in 7-18 pg/L 
of THM4. Pre-chlorination and intermediate chloramination in the lime softening portion of 
plant 8 resulted in the formation of 66-115 pg/L of THM4, whereas only 1-3 pg/L was produced 
in the membrane softening portion of the plant. The combined treated waters at plant 8 after 
final chloramination contained 29-68 pg/L of THM4. Figure 4 shows the seasonal variation in 
THM4 at plant 7 and plant 8 in 2000-2001. THM formation did not vary significantly from 
season to season. 


Figure 4 

Seasonal Variation in Trihalomethanes at Plants 7 and 8 


o> 


x 



120 


100 


9/24/2001 
3/12/2001 


Plant 8 filter 
effluent 


Plant 8 
stripper 
tower eff. 


Plant 8 
plant 
effluent 


Plant 7 
plant 
effluent 


12 / 11/2000 


Even though the source groundwaters contained moderate to high levels of bromide (0.12 
to 0.33 mg/L), chloroform was the dominant THM (e.g., 91 and 81 % of THM4 in SDS testing in 
September 2001 at plant 7 and plant 8, respectively) (Figure 5). In other DBP research, it has 
been shown that bromine speciation is effected by the bromide-to-TOC ratio and the chlorine-to- 
bromide ratio (Symons et al., 1993). In these samples, both the TOC (11-13 mg/L in raw water) 
and chlorine dosages (5-13 mg/L at plant 7 influent; 6-8 mg/L at influent to lime softening 
portion of plant 8) were relatively high. As a result, chlorine was able to effectively compete 
with bromine in forming halogenated DBPs. In addition, low levels of some of the iodinated 
THMs were detected (Figure 5; Tables 10, 16, and 18). Because the concentration of bromide 
was higher at plant 8, this resulted in somewhat more bromine incorporation in the THMs, 
including the formation of a bromine-containing iodinated THM (Figure 5). 


150 






















Figure 5 


Effect of Bromide and Treatment/Disinfection Process on Trihalomethane 
Formation and Speciation in Simulated Distribution System Testing 
(September 24, 2001): Plant 7 Br' = 0.14 mg/L, Plant 8 Br' = 0.25 mg/L 



Haloacids. Chloramination and ozonation at plant 7 resulted in the formation of 21- 
30 pg/L of the five regulated haloacetic acids (HAA5). Pre-chlorination and intermediate 
chloramination in the lime softening portion of plant 8 resulted in the formation of 38-53 pg/L of 
HAA5, whereas only 2-5 pg/L were produced in the membrane softening portion of the plant. 
The combined treated waters at plant 8 after final chloramination contained 17-28 pg/L of 


HAA5. 


In addition, all nine HAAs (HAA9) were measured, which includes all of the brominated 
HAA species. However, HAA9 values were not significantly higher than the levels of HAA5. 
This reflects the relatively low bromine substitution that occurred in these waters. Figure 6 
shows the seasonal variation in HAA9 at plant 7 and plant 8 in 2000-2001. HAA formation did 
not vary significantly from season to season. 

At both plants, the sum of the dihalogenated HAAs (DXAAs) was much higher than the 
sum of the trihalogenated HAAs (TXAAs) (Figure 7). In other DBP research, chloramination 
has been shown to control TXAA formation much better than DXAA formation (Krasner et al., 
1996). In addition, ozonation has been shown to be able to destroy trichloroacetic acid (TCAA) 
precursors better than dichloroacetic acid (DCAA) precursors (Reckhow and Singer, 1984). 
Furthermore, other research has shown that THM formation—in the presence of free chlorine— 
was higher with increasing pH (Stevens et al., 1989). In this same research, pH (in the range of 5 
to 9.4) had no significant effect on DCAA formation, whereas TCAA formation was lower at pH 
9.4 than at the lower pH levels (Stevens et al., 1989). Because chlorine (and chloramines) was 
applied to lime-softened water at plants 7 and 8, pH was a factor in determining which DBPs 


151 








Figure 6 

Seasonal Variation in Haloacetic Acids at Plants 7 and 8 


o> 


< 

< 

X 



9/24/2001 


3/12/2001 


Plant 8 filter 
effluent 


Plant 8 
stripper 
tower eff. 


Plant 8 
plant 
effluent 


12 / 11/2000 


Plant 7 
plant 
effluent 


Figure 7 

Effect of Treatment/Disinfection Process on Trihalomethane and 
Haloacetic Acid Formation at Plants 7 and 8 (September 24, 2001) 



152 
















































formed. Because DXAA formation was higher than THM4 formation at plant 7 in September 
2001, the use of pre-chloramination was probably the major determinant of the relative 
proportion of these DBPs during that sampling date. Because THM4 formation was higher than 
DXAA formation in the softened water at plant 8, the effect of pH was probably the major 
determinant of the relative proportion of these DBPs. 

For example, Figure 8 shows the effect of the disinfection scheme on DBP formation in 
lime-softened waters at plants 7 and 8 for March 12, 2001. At plant 7, chlorine (10 mg/L) and 
ammonia (1.1 mg/L) were added to the raw water that contained 0.69 mg/L of ammonia to begin 
with. At plant 8, on the lime-softening train, chlorine (6.0 mg/L) was added to the raw water. 
Although ammonia was not added at plant 8, the raw water contained 0.62 mg/L of ammonia. 
Therefore, both plants were operating with chloramines, which helped minimized DBP 
formation in this high-TOC groundwater. At plant 8, in the lime-softening portion of the plant, 
additional chlorine (12 mg/L) and ammonia (1.0 mg/L) were added to the softened water. 
Although chloramines were still present, it is possible that the “effective” chlorine-to-nitrogen 
ratio was much higher than in the raw water. At higher chlorine-to-nitrogen ratios, THM 
formation is more likely to occur (Diehl et al., 2000), as evidenced by the relatively high level of 
THMs (98 pg/L) in the filter influent sample at plant 8. 

Figure 8 

Effect of Disinfection Scheme on DBP Formation on 
Lime-Softened Waters at Plants 7 and 8: 3/12/01 


Plant 8/Raw water: 
chlorine dose = 6 mg/L 
total ammonia (raw + 
dose) = 0.6 mg/L 
Filter influent: 
chlorine dose = 12 mg/L 
total ammonia (raw + 
dose) =1.6 mg/L 



TXAAs 
Settled Water ► 


Plant 8 
Plant 7 


DXAAS TXAAs 
Filtered Water-► 


Haloacetonitriles. In other DBP research, haloacetonitriles (HANs) have been found to 
be produced at approximately one-tenth the level of the THMs (Oliver, 1983). HANs were only 
observed at plant 8 in the filter effluent sample in December 2000 and in selected samples at 
both plants in January 2002. HANs can undergo base-catalyzed hydrolysis (Croue and 


153 
























Reckhow, 1989). Because of the high pH of the treated waters at these two plants, most of the 
HANs formed were degraded. None of the target HANs—that were not included in the 
Information Collection Rule (ICR)—were detected in these high-pH samples, except for 
chloroacetonitrile in the SDS sample at plant 8 in September 2001. 

Haloketones. One of the haloketones (HKs) from the ICR—1,1-dichloropropanone 
(1,1-DCP)—was detected at both plant 7 and plant 8, whereas the other ICR HK (1,1,1- 
trichloropropanone) was detected in selected samples at plant 8 and in January 2002 at one 
sample location at plant 7. The latter HK also can undergo base-catalyzed hydrolysis at high pH 
(Croue and Reckhow, 1989). In addition, some of the other target HKs were detected in selected 
samples (Figure 9). 


Figure 9 

Formation of Haloketones at Filter Effluents at Plants 7 and 8 

(September 24, 2001) 



In addition to the target HKs, other HKs were detected in selected samples by the 
broadscreen GC/MS methods (Tables 10 and 16). A number of these HKs were analogous to the 
di- and tetrahalogenated HKs analyzed by MWDSC, except that these were mixed bromochloro 
species. For example, in December 2000, when the raw-water bromide was at 0.12 mg/L, 
MWDSC detected chloropropanone; 1,1-DCP; and 1,1,3,3-tetrabromopropanone (1,1,3,3-TeBP) 
after chloramination and ozonation at plant 7. Broadscreen GC/MS analysis of this same water 
also detected the bromochloro analogue of 1,1-DCP and four bromochloro analogues of 1,1,3,3- 
TeBP. Another HK that was detected at plant 7 by the broadscreen GC/MS methods was 
pentachloropropanone (PCP). MWDSC analysts had attempted to include PCP in its target 
compound list, but PCP degraded immediately and completely in water under all conditions 
evaluated (Gonzalez et al., 2000). 


154 



















Figure 10 


Effect of Disinfection/Treatment Scheme and pH (9-10) on 
Haloacetaldehyde Formation and Stability at Plants 7 and 8: 3/12/01 



- 4 - Filtered Water>■ +— Plant Effluent > 


Haloaldehydes. Chloral hydrate (trichloroacetaldehyde) (an ICR DBP) was detected (2- 
13 pg/L) in the filter effluent sample at plant 8 (Figure 10). Chloral hydrate also undergoes 
base-catalyzed hydrolysis (Stevens et al., 1989) (it is converted to chloroform). Thus, its low 
concentration (0.2-2 pg/L) in the combined treated waters at plant 8 was a result of degradation, 
not only because of dilution with membrane-treated water. In addition, a low level (<3 pg/L) of 
dichloroacetaldehyde (a target DBP) was found at plant 8. 

In contrast, at plant 7, very little chloral hydrate was detected (<1 pg/L), whereas a high 
amount of dichloroacetaldehyde (8-14 pg/L) was detected in the finished water (Figure 10). In 
other DBP research, acetaldehyde (an ozone by-product) was found to react with chlorine to 
form chloroacetaldehyde, which in the presence of free chlorine rapidly reacted to form chloral 
hydrate (McKnight and Reckhow, 1992). At plant 7, chlorine (in the presence of ammonia) may 
have reacted with acetaldehyde formed by the ozonation process to produce dichloro¬ 
acetaldehyde. 

In addition, bromochloroacetaldehyde—a brominated analogue of dichloroacetaldehyde 
—was detected at sub-pg/L levels at two locations at plant 7 in March 2001. The results for 
chloral hydrate in December 2000 represented the sum of the concentrations of chloral hydrate 
and bromochloroacetaldehyde, since these two DBPs co-eluted in the original GC method 
(Krasner et al., 2001). However, based on the March 2001 results, bromochloro-acetaldehyde 
probably did not contribute that much to the December 2000 chloral hydrate results. 


155 












In addition to the target haloaldehydes, two other haloaldehydes were detected in selected 
samples by the broadscreen GC/MS methods (Tables 10 and 16). Dibromoacetaldehyde, the 
fully bromine-substituted analogue of dichloro- and bromochloroacetaldehyde, was detected at 
both plants. Another brominated aldehyde (2-bromo-2-methylpropanal) also was detected at 
both plants. 

Halonitromethanes. Sub-pg/L levels of chloropicrin (trichloronitromethane) (an ICR 
DBP) were detected at selected sites at plant 8 and in January 2002 at plant 7. In addition, some 
of the target halonitromethanes were detected at both plant 7 and plant 8 (Figure 11; Tables 10, 
16, 17, and 18). 


Figure 11 

Formation of Halonitromethanes in Plant Effluents at Plants 7 and 8 

(September 24, 2001) 



Halogenated Furanones. Tables 20 and 21 show results for halogenated furanones in the 
January 2002 sampling for plant 7 and plant 8. Data are included for 3-chloro-4- 
(dichloromethyl)-5-hydroxy-2[5H]-fiiranone, otherwise known as MX; (E)-2-chloro-3- 
(dichloromethyl)-4-oxobutenoic acid, otherwise known as EMX; (Z)-2-chloro-3- 
(dichloromethyl)-4-oxobutenoic acid (ZMX); the oxidized form of MX (Ox-MX); brominated 
forms of MX and EMX (BMXs and BEMXs); and mucochloric acid (MCA), which can be found 
as a closed ring or in an open form. Results are displayed graphically in Figure 12. 

At plant 7 (1/14/02), pre-chloramination and post-ozonation controlled (in part) the 
formation of MX and MX-analogues in a high-TOC (12.6 mg/L) groundwater, as compared 


156 













Halogenated Furanone 
Concentration (pg/L) 


Figure 12 

Plants 7 and 8 (1/14-16/02) 


U BMX-1 

BBEMX-1 

■ BMX-2 

■ BEMX-2 

■ BMX-3 

□ BEMX-3 

■ MX 

HEMX 

■ ZMX 

■ MCA (ring) 

□ MCA (open) 

□ Ox-MX 


2.5U 


2.00 


1.50 


1.00 


0.50 


0.00 




NH3+CI2 




03 


Plant 7 




CI2+NH3 

Sampling 




Point 


CI2+NH3 




<T 

CI2+NH3 


sit 




Jfi- 






Plant 8 


157 







































































to plant 8 (1/16/02) (TOC = 11.3 mg/L) that used lime softening with pre-chlorination in one 
portion of the plant and membranes in the other portion of the plant to control DBP formation 
and remove TOC. Likewise, pre-chlorination in the lime softening portion of plant 8 produced 
more THMs and HAAs than chloramination/ozonation at plant 7 (Figure 7-8). These are the 
results of only one sample event. Additional measurements of membrane-treated water should 
be conducted in the future to determine whether these results are repeatable. However, the 
significant brominated MX-analogue production in plant 8 is consistent with the high-bromide, 
source-water quality (0.27 mg/L in the raw water and 0.1 mg/L in the membrane effluent). 

Volatile Organic Compounds (VOCs). In December 2000, carbon tetrachloride was 
detected in one sample (distribution system of plant 7) just above its MRL (0.06 pg/L). In 
March 2001, this compound was found in all of the samples (0.2-0.7 pg/L) except for the raw 
waters and the effluent of the stripping towers (i.e., membrane-softened water). In September 
2001, it was not detected in any of the samples with an MRL of 0.2 pg/L. In January 2002, 
carbon tetrachloride was detected in one sample (distribution system) of plant 7 at the revised 
MRL (0.2 pg/L) and in several samples at plant 8 (0.2-0.6 pg/L). Carbon tetrachloride is a VOC 
and a possible DBP. Carbon tetrachloride has been detected by some utilities in gaseous chlorine 
cylinders (EE&T, 2000). Incidents of carbon tetrachloride contamination have been traced to 
either imperfections in the manufacturing process or improper cleaning procedures. Carbon 
tetrachloride is used to clean out cylinders before filling with chlorine. If carbon tetrachloride is 
not allowed sufficient time to evaporate, it can contaminate the chlorine. 

In September 2001, methyl ethyl ketone (MEK) was detected in selected samples at 0.9- 
1 pg/L. In January 2002, MEK was detected after ozonation at plant 7 (0.6-0.9 pg/L) and in two 
samples at plant 8 (<0.5-1 pg/L). MEK is a VOC and a possible DBP. Also in January 2002, 
methyl tertiary butyl ether (MTBE) was detected (0.3 pg/L) in one sample (stripper tower 
effluent) of plant 8 just above its MRL (0.2 pg/L). MTBE is a VOC, not a DBP. 

Other Halogenated DBPs. A few additional, miscellaneous halogenated DBPs were also 
detected. UNC methods detected dichloroacetamide at 1.8 and 2.1 pg/L in finished waters from 
plant 7 and plant 8, respectively, in March 2001 (Table 13). In addition, the concentration of 
dichloroacetamide increased in SDS testing. In samples collected in January 2002, 
dichloroacetamide, dibromoacetamide, and trichloroacetamide were found in finished waters 
from both treatment plants at levels for individual species ranging from 0.1 to 3.0 pg/L (Table 
19). The concentrations of these latter compounds either increased or remained steady in the 
distribution system. Broadscreen GC/MS analyses revealed the presence of 
hexachlorocyclopentadiene and bromopentachlorocyclopentadiene in finished water from plant 7 
in December 2000 (Table 10) and plant 8 in September 2001 (Table 16). These compounds were 
not observed in the corresponding raw, untreated water. 

Non-Halogenated DBPs. A few non-halogenated DBPs were also detected in finished 
waters from plants 7 and 8. Dimethylglyoxal was identified at 3.5 pg/L in finished waters from 
plant 7 in March 2001 (Table 13) and in finished waters at 2.8 pg/L from plant 7 in January 2002 
(Table 19). Broadscreen GC/MS analysis also revealed the presence of formaldehyde, acetone, 
glyoxal, and methyl glyoxal in plant 7 finished waters in December 2002, and acetone, propanal, 
2-butanone, 3-hexanone, 2-hexanone, glyoxal, and methyl glyoxal in finished waters from plant 


158 


8 in September 2001 (Table 16). Several non-halogenated carboxylic acids were also observed 
in the finished waters at significantly higher levels than found in the raw, untreated water (Table 
16). 


Other DBP Formation and Stability Issues. Figures 13-14 show the effect of seasonal 
variations on DBP formation at plant 7 (plant effluent) and at plant 8 (filter effluent). 
Essentially, there did not appear to be any significant seasonal variations in water quality, 
operations or DBP formation at either of these two treatment plants. 

Figure 13 

Effect of Seasonal Variations on DBP Formation at Plant 7: 

Plant Effluent 



159 












Figure 14 


Effect of Seasonal Variations on DBP Formation at Plant 8: 

Filter Effluent 


O) 


CL 

CO 

Q 


At plant 7, HAA formation (the sum of all nine species) was greater than THM formation 
(on a weight basis). The haloacetaldehydes were the third largest fraction (by weight) of 
halogenated DBPs. At plant 7, most of the haloacetaldehyde formation was due to dichloro- 
acetaldehyde (a target DBP) and not due to chloral hydrate (an ICR DBP). HAN formation was 
quite small. 

Alternatively, at plant 8, THM formation was greater than HAA formation. The 
haloacetaldehydes and HANs were the third and fourth largest fractions of halogenated DBPs. 
The formation of the latter two fractions was higher in December 2000 than in March 2001. 
During the December 2000 sampling, the pH of the settled water and filter effluent were 9.7 and 
9.2, respectively, whereas during the March 2001 sampling, the pH of the settled water and filter 
effluent were 10.4 and 10.0, respectively. Because chloral hydrate and dichloroacetonitrile (the 
major components of the latter two fractions at plant 8, respectively) both undergo base- 
catalyzed hydrolysis, their formation may have been lower in March 2001 because of the 
somewhat higher pH. 

Figure 15 shows the effect of blending lime-softened water (filter effluent) with 
membrane-softened water (effluent of stripper towers) and base-catalyzed hydrolysis on DBP 
concentrations in the plant effluent of plant 8 on September 24, 2001. The flows of the lime¬ 
softening and membrane-softening portions of the plant were 3.3 and 6.8 mgd, respectively. For 
the TXAAs, 8.9 pg/L was detected in the lime-softened water, whereas none was detected in the 
membrane-softened water. Based on blending, using the flows of each portion of the treatment 
plant, one would expect the TXAAs to be diluted down to 2.9 pg/L. In the actual plant effluent, 
there was 3.2 pg/L of TXAAs. In contrast, the theoretical levels of dichloroacetonitrile 



160 























(0.8 pg/L) and of chloral hydrate (1.1 pg/L) were greater than the measured values (i.e., 0.5 and 
0.3 pg/L, respectively). As discussed previously, the lower measured values—especially for 
chloral hydrate—were due to base-catalyzed hydrolysis. On the other hand, the theoretical levels 
of DXAAs (11 pg/L) and of THM4 (25 pg/L) were significantly less than the measured values 
(i.e., 21 and 41 pg/L, respectively). These latter DBPs continued to form downstream of 
blending (and after additional chlorine addition). In addition, when chloral hydrate is 
hydrolyzed, chloroform (one of the THMs) is formed. Thus, some of the formation may also be 
due to the breakdown of other unstable DBPs (at least unstable at pH 9). Finally, 
dichloroacetaldehyde was relatively conservative (theoretical and measured values of 0.7 and 
0.9 pg/L, respectively). Therefore, it did not undergo base-catalyzed hydrolysis as the chloral 
hydrate (trichloroacetaldehyde) did. 


Figure 15 


Effect of Blending and pH on Formation and Stability of DBPs at 

Plant 8 (September 24, 2001) 



161 























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Stevens, A. A., L. A. Moore, and R. J. Miltner. Formation and control of non-trihalomethane 
disinfection by-products. .Journal of the American Water Works Association 81 (8):54 (1989). 

Symons, J. M., S. W. Krasner, L. A. Simms, and M. J. Sclimenti. Measurement of THM and 
precursor concentrations revisited: the effect of bromide ion. Journal of the American Water 
Works Association 85(1):51 (1993). 

van der Kooij, D., A. Visser, and W. A. M. Hijnen. Determining the concentration of easily 
assimilable organic carbon in drinking water. Journal of the American Water Works Association 
74(10):540 (1982). 


163 


EPA REGION 4: PLANTS 5 AND 6 


Plant Operations and Sampling 

Plant 5 and plant 6 in EPA Region 4 treated water from the same river. On November 
27, 2000, February 26, 2001, August 13, 2001, October 22, 2001, and April 15, 2002, these two 
plants were sampled 

Plant 5 was an ozone plant (Figure 1). This plant consisted of two facilities operating 
simultaneously and parallel to one another: 

• One was a conventional facility. After raw-water ozonation, the water underwent 
flocculation, coagulation, and sedimentation. The settled water then underwent intermediate 
ozonation. Ozonated settled water then entered biologically-activated filters, composed of 
granulated activated carbon (GAC) over sand. 

• The other facility utilized solids contact - upflow clarification of coagulated water (Super 
Pulsator technology) following ozonation of the raw water. After clarification, the settled 
water underewent intermediate ozonation. Ozonated settled water then entered biologically 
activate filters, composed of deep-bed GAC filters. 

Effluents from all of the filters were combined and final chemical adjustments were made. This 
included the addition of sodium hypochlorite for secondary disinfection and residual 
maintenance. Finished water then flowed first into one and then another closed reservoir for 
storage prior to being pumped into the distribution system. 

Figure 1 

Plant 5 Schematic 



164 







































Plant 5 was sampled at the following locations: 

(1) raw water 

(2) the effluent of the raw-water ozone contactor 

(3) the GAC/sand influent on the conventional train 

(4) the GAC/sand effluent on the conventional train 

(5) the GAC influent on the Super Pulsator train 

(6) the GAC effluent on the Super Pulsator train 

(7) the composite filter effluent (on selected dates) 

(8) the plant effluent 

In addition, plant effluent was collected and simulated distribution system (SDS) testing was 

conducted for average and maximum detention times (Table 1). Furthermore, the distribution 

system was sampled at two locations, one representing an average detention time and the other 

representing a maximum detention time. 

Plant 6 was a chlorine dioxide plant (Figure 2): 

• After disinfection of the raw water with chlorine dioxide, the water underwent coagulation 
and clarification. The settled water was then chlorinated and filtered. Filtered water was 
then chloraminated and distributed. 

• Starting with the August 2001 sampling, plant 6 moved their chlorine dioxide feed point up¬ 
stream of the plant. In November 2000 and February 2001, chlorine dioxide had been fed at 
the flash mixers. Plant 6 gained approximately 7-10 minutes of contact time (depending on 
flow) by adding the new feed point. 


Figure 2 


Plant 6 Schematic 


River 


chlorine 



165 














Plant 6 was sampled at the following locations: 

(1) raw water 

(2) settled water 

(3) filter effluent 

(4) clearwell effluent 

(5) the plant effluent 

In addition, plant effluent was collected and SDS testing was conducted for average and 
maximum detention times for that time of the year. Furthermore, the distribution system was 
sampled at two locations, one representing an average detention time and the other representing a 
maximum detention time. 


Table 1. SDS holding times (days) at plants 5 and 6 


Sample 

11/27/00 

2/26/01 

8/13/01 

10/22/01 

4/15/02 

Plant 5 average detention time 

2.9 

2.9 

3.1 

4 

5.3 

Plant 5 maximum detention time 

6 

6 

7 

8 

7 

Plant 6 average detention time 

4 

4 

4 

4 

3 

Plant 6 maximum detention time 

7 

7 

7 

7 

7 


On the day of sampling, information was collected on the operations at each plant 
(Tables 2-3). 


Table 2. Operational information at plant 5 


Parameter 

11/27/00 

2/26/01 

8/13/01 

10/22/01 

4/15/02 

Overall plant flow (mgd) 

25 a 

12.3 

19.35 

17.26 

17.4 

Plant flow for conventional coag. train (mgd) 

15 a 

6.0 

9.97 

9.41 

7.59 

Plant flow for Super Pulsator train (mgd) 

10 a 

6.3 

9.38 

7.85 

9.81 

Raw-Water Ozone Contactor 






Ozone dose (mg/L) 

4.33 

3.4 

3.90 

2.80 

4.50 

CT (mg/L-min) achieved from ozonation 

NA b 

NA 

NA 

NA 

9.0 

Conventional Train 






Coagulanf (mg/L) 

29.5 

31 

41.6 

40.5 

40.32 

Ozone dose (mg/L) 

3.98 

1.0 

2.30 

2.20 

2.52 

Hydraulic retention time (t i0 ) in ozone contactor 
(min) 

~20 

~20 

~20 

~20 

~20 

CT (mg/L-min) achieved from ozonation 

NA 

NA 

NA 

7.0 

7.0 

GAC/sand filter loading rate (gpm/sq ft) 

1.18 

0.96 

1.63 

1.47 

1.25 

Super Pulsator Train 






Coagulant (mg/L) 

38.4 

29 

46.7 

45.7 

45.4 

Ozone dose (mg/L) 

2.03 

0.5 

1.50 

0.90 

2.52 

1 1 o in ozone contactor (min) 

~20 

~20 

20 

20 

20 

CT (mg/L-min) achieved from ozonation 

NA 

NA 

NA 

7.0 

7.0 

GAC filter loading rate (gpm/sq ft) 

1.29 

1.9 

3.13 

2.65 

3.38 

Composite Filter Effluent 






Chlorine dose at filter effluent (mg/L as CL) 

1.7 

1.8 

4.0 

4.1 

2.53 

Chlorine dose at clearwell effluent (mg/L as Cl 2 ) 

~2.0 

1.6 

1.5 

1.9 

1.02 

a Design flows ^NA = Not available c Alum 

[A1 2 (S0 4 ) 3 14H 2 0] 


166 













































Table 3. Operational information at plant 6 


Parameter 

11/27/00 

2/26/01 

8/13/01 

10 / 22/01 

4/15/02 

Plant flow (mgd) 

8 

8.2 

9 

8 

7 

Coagulant 3 (mg/L wet; 
mg/L dry) 

16 

18 

38; 

~19 

32; 

16 

53; 

26.5 

Chlorine dioxide dose (mg/L as CIO 2 ) 

1.95 

1.5 

1.98 

2.1 

1.5 

Chlorine dose at filter influent (mg/L as CI 2 ) 

0.60 

0.66 

2.5 

1.5 

1.11 

Chlorine dose at clearwell eff. (mg/L as CI 2 ) 

3.2 

2.5 

2.7 

3.0 

3.0 

Ammonia dose at plant eff. (mg/L as NH 3 -N) 

1.0 

0.76 

0.87 

1.0 

1.0 


a PAX 18 polyaluminum chloride [Al(OH)Cl] (17 % as AI 2 O 3 ) 


Water Quality 

On the day of sampling, information was also collected on the water quality at each plant 
(Tables 4-5). 

Data were collected for total organic carbon (TOC) and ultraviolet (UV) absorbance 
(Tables 6-7). The TOC ranged from 6.2 to 10 mg/L at plant 5 and from 6.4 to 10 mg/L at plant 
6 . The UV was 0.19 to 0.35 cm ' 1 at plant 5 and was 0.19 to 0.30 cm ' 1 at plant 6 . 

At plant 5, pre-ozonation reduced the level of TOC by 0-29 %, whereas the UV was 
reduced by 20-67 %. In the Super Pulsator treatment train, coagulation removed 43-54 % of the 
TOC and GAC filtration removed another 5-23 %. Coagulation reduced the UV by 63-83 %. 

The overall (cumulative) removal of TOC at the Super Pulsator treatment train—including from 
pre-ozonation—was 58-65 %, and the UV reduction was 85-93 %. The overall (cumulative) 
removal of TOC at the conventional train—including from pre-ozonation—was 62-69 %, and the 
UV reduction was 85-95 %. 

At plant 6 , coagulation removed 38-57 % of the TOC and filtration removed another 4-7 
%. Coagulation reduced the UV by 68-77 %. 

Table 8 shows the values of miscellaneous other water quality parameters in raw water at 
the two plants. Bromide ranged from 0.05 to 0.08 mg/L at plant 5 and from 0.04 to 0.08 mg/L at 
plant 6 . For plant 5, the raw water was collected 23 miles upstream to eliminate the intake of 
salty water due to tidal changes. However, the presence of bromide in the raw water, which was 
higher in concentration in the fall, may indicate some saltwater intrusion. 

The source water was low in alkalinity. Because of the low alkalinity, settled water (after 
the addition of coagulant) was acidic (Tables 4-5). 


167 














Table 4. Water quality information at plant 5 



pH 

Temperature (°C) 

Disinfectant Residual 3 (mg/L) 

Location b 

11/27/00 

2/26/01 

8/13/01 

10/22/01 

4/15/02 

11/27/00 

2/26/01 

8/13/01 

10/22/01 

4/15/02 

11/27/00 

2/26/01 

8/13/01 

10/22/01 

4/15/02 

Raw water 

6.8 

6.5 

6.4 

6.6 

6.2 

13.8 

16 

29 

21 

21 

— 

— 

— 

— 

— 

Pre-0 3 eff. 

6.8 

6.6 

6.4 

6.5 

6.2 

13.0 

16 

29 

22 

21 

ND C 

ND 

ND 

ND 

ND 

Conventional Train 

GAC/s inf. 

5.8 

5.6 

5.7 

5.8 

5.6 

11.9 

13 

29 

21 

21 

ND d 

0.05 

0.08 

0.1 

0.09 

GAC/s eff. 

5.9 

5.6 

5.7 

5.9 

5.7 

12.0 

13 

29 

22 

20 

— 

— 

— 

— 

— 

Super Pulsator Train 

GAC inf. 

5.9 

5.7 

5.7 

5.7 

5.6 

11.9 

12 

29 

21 

21 

ND d 

0.04 

0.09 

0.08 

0.1 

GAC eff. 

5.9 

5.6 

5.7 

5.7 

5.6 

12.0 

13 

29 

22 

21 

— 

— 

— 

— 

— 

Composite Filter Effluent 

Filter eff. 

5.9 

NS' 

NS 

NS 

NS 

13.4 

NS 

NS 

NS 

NS 

— 

NS 

NS 

NS 

NS 

Plant eff. 

7.0 

7.0 

7.0 

7.1 

7.0 

15.8 

16 

29 

22 

20 

2.0 

1.6 

1.7 

1.5 

1.6 

DS/ave. 

7.0 

7.5 

7.0 

7.5 

7.0 

15 

12 

28 

24.9 

18 

1.8 

0.8 

1.2 

0.4 

1.0 

DS/max. 

7.5 

7.5 

7.0 

7.5 

7.5 

15 

11 

28 

23.2 

18 

0.2 

0.8 

<0.1 

0.3 

<0.1 

SDS/ave. 

7.2 

6.8 

7.0 

7.0 

6.8 

18 

19 

23.5 

23 

23 

1.8 

0.5 

1.0 

0.9 

<0.1 

S DS/max. 

7.2 

6.7 

7.0 

7.1 

7.2 

18 

20 

25.0 

23 

24 

0.3 

0.04 

0.6 

0.5 

<0.1 


“Ozone residuals (values shown in bold) in effluent of raw-water ozone contactor and in effluents of intermediate ozone contactors at GAC/sand and GAC influents; 
chlorine residuals at plant effluent, in distribution system, and in SDS testing. 
b Pre-0 3 = raw-water ozone contactor, GAC/s = GAC/sand, DS = distribution system. 

C ND = Not detected. 

d Ozone sequestered with hydrogen peroxide prior to filtration. 

'NS = Not sampled. 


Table 5. Water quality information at plant 6 



PH 

Temperature (°C) 

Disinfectant Residual 3 (mg/L) 

Location 6 

11/27/00 

2/26/01 

8/13/01 

10/22/01 

4/15/02 

11/27/00 

2/26/01 

8/13/01 

10/22/01 

4/15/02 

11/27/00 

2/26/01 

8/13/01 

10/22/01 

4/15/02 

Raw water 

7.0 

6.9 

6.5 

7.0 

6.7 

13.0 

13.6 

28.4 

19.9 

18 

— 

0.2 

— 

— 

— 

Settled 

6.6 

6.4 

6.2 

6.7 

6.2 

13.4 

13.8 

27.3 

19.8 

20.2 

ND/0.2 

0.04 

0.02 

.05 10.2 

ND 

Filter eff. 

6.5 

6.7 

7.4 

7.5 

8.0 

13.0 

12.6 

28.1 

20.3 

19.9 

ND/0.4 

0.3 

0.5/.01 

2.0 

0.2 

Clearwell 

7.0 

6.8 

6.9 

7.1 

6.9 

12.8 

12.4 

28.5 

20.1 

19.0 

0.03/2.2 

1.7 

2 . 6 /m 

2.2 

2.9 

Plant eff. 

7.1 

6.8 

7.2 

7.2 

7.1 

13.9 

12.5 

27.4 

20.5 

20.9 

2.2-2.6 

2.2 

2.9/.05 

2.6 

3.2 

DS/ave. 

7.3 

7.2 

7.1 

7.9 

6.8 

12.0 

12.0 

27 

21.0 

18.4 

2.0 

1.7 

2.2 

1.4 

3.2 

DS/max. 

7.7 

7.4 

7.5 

8.1 

7.4 

13.0 

12.0 

26 

21.0 

18.3 

0.9 

1.2 

1.5 

1.3 

1.8 

SDS/ave. 

7.3 

NA 

7.3 

7.0 

7.2 

5.0 

NA 

28.5 

20.3 

21.8 

2.1 

NA 

1.3 

1.9 

>2.2 

S DS/max. 

7.1 

NA 

7.2 

7.0 

6.9 

5.0 

NA 

27.9 

19.4 

22.6 

1.7 

NA 

1.1 

1.4 

2.0 


“Chlorine dioxide residuals (values shown in bold) and chlorine residuals (values shown in italics) in raw water, settled water, filter effluent, clearwell effluent, and plant 
effluent; chloramine residuals (total chlorine residual as CI 2 ) at plant effluent, in distribution system, and in SDS testing. 
b DS = Distribution system 


168 















































































































Table 6. TOC and UV removal at plant 5 


Location 

TOC 

(mg/L) 

UV a 

(cm' 1 ) 

SUVA b 

(L/mg-m) 

Remova 

/Unit (%) 

Removal/Cumulative (%) 

TOC 

UV 

TOC 

UV 

11/27/2000 








Raw 

6.23 

0.204 

3.27 

— 

— 

— 

— 

Pre-Ozone Eff. 

6.07 

0.157 

2.59 

2.6% 

23% 

2.6% 

23% 

GAC/Sand Inf. 

3.22 

0.024 

0.75 

47% 

85% 

48% 

88% 

GAC/Sand Eff. 

2.24 

0.019 

0.85 

30% 

21% 

64% 

91% 

GAC Inf. 

2.88 

0.026 

0.90 

53% 

83% 

54% 

87% 

GAC Eff. 

2.22 

0.019 

0.86 

23% 

27% 

64% 

91% 

02/26/2001 








Raw 

7.44 

0.244 

3.28 

— 

— 

— 

— 

Pre-Ozone Eff. 

7.45 

0.196 

2.63 

-0.1% 

20% 

-0.1% 

20% 

GAC/Sand Inf. 

NR b 

0.036 

NA 

NA 

82% 

NA 

85% 

GAC/Sand Eff. 

2.81 

0.030 

1.07 

NA 

17% 

62% 

88% 

GAC Inf. 

3.41 

0.035 

1.03 

54% 

82% 

54% 

86% 

GAC Eff. 

3.14 

0.033 

1.05 

7.9% 

5.7% 

58% 

86% 

08/13/2001 








Raw 

7.26 

0.251 

3.46 

— 

— 

— 

— 

Pre-Ozone Eff. 

5.18 

0.082 

1.58 

29% 

67% 

29% 

67% 

GAC/Sand Inf. 

4.46 

0.020 

0.45 

14% 

76% 

39% 

92% 

GAC/Sand Eff. 

2.26 

0.013 

0.58 

49% 

35% 

69% 

95% 

GAC Inf. 

2.94 

0.023 

0.78 

43% 

72% 

60% 

91% 

GAC Eff. 

2.8 

0.018 

0.64 

4.8% 

22% 

61% 

93% 

10/22/2001 








Raw 

6.74 

0.192 

2.85 

— 

— 

— 

— 

Pre-Ozone Eff. 

5.26 

0.082 

1.56 

22% 

57% 

22% 

57% 

GAC/Sand Inf. 

3.22 

0.029 

0.90 

39% 

65% 

52% 

85% 

GAC/Sand Eff. 

2.45 

0.028 

1.14 

24% 

3.4% 

64% 

85% 

GAC Inf. 

2.87 

0.030 

1.05 

45% 

63% 

57% 

84% 

GAC Eff. 

2.66 

0.029 

1.09 

7.3% 

3.3% 

61% 

85% 

04/15/2002 








Raw 

10.28 

0.351 

3.41 

— 

— 

— 

— 

Pre-Ozone Eff. 

8.66 

0.133 

1.54 

16% 

62% 

16% 

62% 

GAC/Sand Inf. 

4.44 

0.036 

0.81 

49% 

73% 

57% 

90% 

GAC/Sand Eff. 

3.36 

0.030 

0.89 

24% 

17% 

67% 

91% 

GAC Inf. 

3.95 

0.039 

0.99 

54% 

71% 

62% 

89% 

GAC Eff. 

3.64 

0.036 

0.99 

7.8% 

7.7% 

65% 

90% 


a UV = Ultraviolet absorbance reported in units of "inverse centimeters" (APHA, 1998) 
b SUVA (L/mg-m) = Specific ultraviolet absorbance = 100*UV (cm'^/DOC (mg/L) or UV (m'^/DOC (mg/L), 
where DOC = dissolved organic carbon, which typically = 90-95% TOC (used TOC values in calculating SUVA) 
(e.g., UV = 0.204/cm = 0.204/(0.01 m) = 20.4/m, DOC = 6.23 mg/L, SUVA = (20.4 m' 1 )/^^ mg/L) = 3.27 L/mg-m) 
b NR = Not reported; sample very turbid (white cloudy material that stayed in suspension) 


169 














































Table 7. TOC and UV removal at plant 6 

—■ i\ /3 


Location 

TOC 

(mg/L) 

UV a 

(cm' 1 ) 

SUVA b 

(L/mg-m) 

Removal/Unit (%) 

Removal/Cumulative (%) 

TOC 

UV 

TOC 

UV 

11/27/2000 








Raw 

6.36 

0.210 

3.30 

— 

— 

— 

— 

Settled Water 

3.76 

0.062 

1.65 

41% 

70% 

41% 

70% 

Filter Eff. 

3.51 

0.058 

1.65 

6.6% 

6.5% 

45% 

72% 

02/26/2001 








Raw 

8.09 

0.261 

3.23 

— 

— 

— 

— 

Settled Water 

4.24 

0.070 

1.65 

48% 

73% 

48% 

73% 

Filter Eff. 

3.99 

0.069 

1.73 

5.9% 

1.4% 

51% 

74% 

08/13/2001 








Raw 

7.86 

0.264 

3.36 

— 

— 

— 

— 

Settled Water 

4.7 

0.085 

1.81 

40% 

68% 

40% 

68% 

Filter Eff. 

4.53 

0.070 

1.55 

3.6% 

18% 

42% 

73% 

10/22/2001 








Raw 

6.66 

0.189 

2.84 

— 

— 

— 

— 

Settled Water 

4.16 

0.071 

1.71 

38% 

62% 

38% 

62% 

Filter Effluent 

3.93 

0.066 

1.68 

5.5% 

7.0% 

41% 

65% 

04/15/2002 








Raw 

9.5 

0.305 

3.21 

— 

— 

— 

— 

Settled Water 

4.07 

0.070 

1.72 

57% 

77% 

57% 

77% 

Filter Effluent 

3.88 

0.062 

1.60 

4.7% 

11% 

59% 

80% 


Table 8. Miscellaneous water quality parameters in raw water at plant 5 and plant 6 

Plant 5 Plant 6 


Date 

Bromide 

(mg/L) 

Alkalinity 

(mg/L) 

Ammonia 
(mg/L as N) 

11/27/2000 

0.08 

26 

ND 

02/26/2001 

0.047 

22 

ND 

08/13/2001 

0.06 

19 

ND 

10/22/2001 

0.08 

28 

0.04 

04/15/2002 

0.06 

20 

0.08 


Date 

Bromide 

(mg/L) 

Alkalinity 

(mg/L) 

Ammonia 
(mg/L as N) 

11/27/2000 

0.08 

25 

ND 

02/26/2001 

0.039 

21 

0.08 

08/13/2001 

0.05 

20 

ND 

10/22/2001 

0.08 

27 

ND 

04/15/2002 

0.06 

20 

0.05 


DBPs 


Oxyhalides. Tables 9-10 show the formation of oxyhalides at the two plants. At plant 5, 
ozonation resulted in the formation of from <3 to 6 pg/L of bromate when bromate was detected 
(Table 9). The conversion of bromide to bromate—when bromate was detected—was 2-5 % (on 
a molar basis), which is a typical conversion rate for an ozone plant operating for Giardia 
inactivation (Douville and Amy, 2000). Because the pH of ozonation was acidic (Table 4), 
bromate was often not detected, since low-pH ozonation minimizes bromate formation (Krasner 


170 


















































Table 9. Oxyhalide formation at Plant 5 


Location 

Bromate 3 

(pg/L) 

Chlorate 

(pg/L) 

Bromate/Bromide 

(pmol/pmol) 

11/27/2000 




Pre-Ozone Eff. 

ND 

5.8 

— 

Plant Eff. 

3.8 

79 

3.0% 

02/26/2001 




Pre-Ozone Effl. 

ND 

4.6 

— 

GAC/Sand Inf. 

ND 

8.4 

— 

GAC Inf. 

ND 

5.7 

— 

Plant Eff. 

ND 

45 

— 

08/13/2001 




Pre-Ozone Effl. 

5 

5 

5.2% 

GAC/Sand Inf. 

ND 

12 

— 

GAC Inf. 

ND 

14 

— 

Plant Eff. 

ND 

245 

— 

10/22/2001 




Pre-Ozone Effl. 

5.6 

ND 

4.4% 

GAC/Sand Inf. 

2.1 

ND 

1.6% 

GAC Inf. 

ND 

ND 

— 

Plant Eff. 

1.9 

162 

1.5% 

04/15/2002 




Pre-Ozone Effl. 

3.5 

ND 

3.6% 

GAC/Sand Inf. 

2.2 

ND 

2.3% 

GAC Inf. 

ND 

ND 

— 

Plant Eff. 

2.98 

184 

3.1% 


Reporting detection level (RDL) for bromate = 3 |jg/L; 
value in italics < RDL 


Table 10. Oxyhalide formation at Plant 6 


Location 

Chlorite 

(pg/L) 

Chlorate 

(pg/L) 

CI0 2 7CI0 2 

% 

11/27/2000 




Settled Water 

1180 

106 

61% 

Plant Eff. 

1300 

146 

67% 

02/26/2001 




Settled Water 

783 

69 

51% 

Plant Eff. 

651 

77 

43% 

08/13/2001 




Settled Water 

772 

137 

39% 

Clearwell Eff. 

697 

283 

35% 

10/22/2001 




Settled Water 

1300 

90 

62% 

Plant Eff. 

1040 

184 

50% 

04/15/2002 




Settled Water 

765 

100 

51% 

Plant Eff. 

694 

139 

46% 


171 
















































et al., 1993). In addition, sodium hypochlorite can be contaminated with low or sub-pg/L levels 
of bromate (Delcomyn et al., 2000). Because the reporting detection level for bromate was 3 
pg/L, it was not possible to determine if there was a significant increase in the concentration of 
bromate in the treated water after secondary disinfection. Low levels (<15 pg/L) of chlorate 
were detected at plant 5 until the plant effluent (Table 9). Chlorate was primarily introduced into 
the finished water after the secondary disinfection (chlorate is a by-product formed during the 
decomposition of the hypochlorite stock solution [Bolyard et al. [1992]). 

It has been reported that during water treatment, approximately 50-70 % of the chlorine 
dioxide (CIO 2 ) reacted will immediately appear as chlorite (CIO 2 ') and the remainder as chloride 
(Aieta and Berg, 1986). An amount of chlorite consistent with this report was detected at plant 6 
in the settled water (Table 10). The residual chlorite can continue to degrade in the water 
system. At plant 6, the concentration of chlorite was typically somewhat lower in the plant 
effluent, whereas the level of chlorate was somewhat higher. 

Biodegradable Organic Matter. Ozone can convert natural organic matter in water to 
carboxylic acids (Kuo et al., 1996) and other assimilable organic carbon (AOC) (van der Kooij et 
al., 1982). Table 11 shows the carboxylic acid and AOC data for plant 5. Because AOC data are 
expressed in units of micrograms of carbon per liter (pg C/L), the carboxylic acid data were 
converted to the same units. A portion of the molecular weight (MW) of each carboxylic acid is 
due to carbon atoms (i.e., 27-49 %), and the remainder due to oxygen and hydrogen atoms. The 
sums of the five carboxylic acids (on a pg C/L basis) were compared to the AOC data. On a 
median basis for each sample date, 29 to 70 % of the AOC was accounted for by the carboxylic 
acids. For the raw-water sample in February 2001, »100 % of the AOC was accounted for by 
the carboxylic acids. Because the amount of AOC in the raw water was low, this comparison 
was not as accurate as for the other samples in the plant. 

Pre-ozonation significantly increased the concentration of the carboxylic acids (Table 11, 
Figure 3). In August 2001 (and in October 2001 and April 2002), formation of carboxylic acids 
(e.g., oxalate) was much higher during pre-ozonation (Table 11, Figure 4). The concentrations 
of the carboxylic acids were significantly decreased in both trains prior to the filters in August 
2001 (Figure 3) (and in October 2001 and April 2002 [Table 11]). In the previous two 
samplings, the concentration of most of the carboxylic acids (e.g., oxalate) increased after 
intermediate ozonation (e.g., see GAC/sand influent data) (Figure 4). In the August 2001, 
October 2001, and April 2002 samplings, some of the carboxylic acids may have been removed 
during the coagulation process and/or biodegraded in the basins (Volk and LeChevallier, 2002). 
Biological filtration on the GAC/sand filters in the conventional treatment train and the GAC 
filters in the Super Pulsator treatment train resulted in further removal of the carboxylic acids 
that were present in the filter influent (Table 11, Figures 3-4). Moreover, the residual amount of 
carboxylic acids (e.g., oxalate) in the filtered water was somewhat similar in each season 
regardless of the level produced by the ozonation process (Table 11, Figure 3). 


172 


Table 11. Formation and removal of carboxylic acids and AOC at plant 5 


Location 

Concentration 3 (uq/L) 

Concentration (pq C/L) 

Sum/ 

AOC 

Acetate 

Propionate 

Formate 

Pyruvate 

Oxalate 

Acetate 

Propionate 

Formate 

Pyruvate 

Oxalate 

Sum 

AOC 

11/27/2000 














Raw 

5.0 

6.5 

8.3 

ND b 

17 

2.0 

3.2 

2.2 

ND 

4.7 

12 

18 

68% 

Pre-Ozone Eff. 

37 

ND 

120 

38 

185 

15 

ND 

32 

16 

50 

113 



GAC/Sand Inf. 

127 

9.4 

244 

20 

328 

52 

4.6 

65 

8.3 

89 

219 

420 

52% 

GAC/Sand Eff. 

19 

ND 

50 

19 

52 

7.6 

ND 

13 

8.0 

14 

43 



GAC Inf. 

98 

ND 

202 

ND 

220 

40 

ND 

54 

ND 

60 

154 

428 

36% 

GAC Eff. 

18 

ND 

38 

17 

51 

7.4 

ND 

10 

7.2 

14 

38 

349 

11% 













median 

44% 

02/26/2001 














Raw 

20 

ND 

42 

22 

43 

8.1 

ND 

11 

9.1 

12 

40 

13 

310% 

Pre-Ozone Eff. 

28 

ND 

34 

27 

398 

11 

ND 

9.1 

11 

109 

140 



GAC/Sand Inf. 

136 

ND 

313 

79 

468 

55 

ND 

83 

33 

128 

299 

430 

70% 

GAC/Sand Eff. 

31 

ND 

66 

26 

67 

13 

ND 

18 

11 

18 

59 



GAC Inf. 

NR C 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

331 


GAC Eff. 

15 

ND 

22 

ND 

72 

6.1 

ND 

5.9 

ND 

20 

32 

237 

13% 













median 

70% 

08/13/2001 














Raw 

17 

ND 

11 

ND 

24 

6.9 

ND 

2.9 

ND 

6.5 

16 

38 

44% 

Pre-Ozone Eff. 

600 

ND 

880 

94 

1800 

244 

ND 

235 

39 

491 

1009 



GAC/Sand Inf. 

156 

ND 

264 

53 

472 

63 

ND 

70 

22 

129 

285 

329 

87% 

GAC/Sand Eff. 

37 

ND 

57 

8.5 

49 

15 

ND 

15 

3.5 

13 

47 



GAC Inf. 

54 

ND 

78 

19 

159 

22 

ND 

21 

7.9 

43 

94 

218 

43% 

GAC Eff. 

32 

ND 

44 

13 

58 

13 

ND 

12 

5.4 

16 

46 

87 

53% 













median 

48% 

10/22/2001 














Raw 

9.6 

ND 

8.1 

ND 

16 

3.9 

ND 

2.2 

ND 

4.4 

10 

31 

34% 

Pre-Ozone Eff. 

174 

3.1 

367 

82 

857 

71 

1.5 

98 

34 

234 

438 



GAC/Sand Inf. 

111 

ND 

193 

37 

312 

45 

ND 

51 

15 

85 

197 

759 

26% 

GAC/Sand Eff. 

21 

ND 

40 

8.4 

45 

8.5 

ND 

11 

3.5 

12 

35 



GAC Inf. 

25 

ND 

52 

9.7 

66 

10 

ND 

14 

4.0 

18 

46 

161 

29% 

GAC Eff. 

37 

ND 

36 

7.1 

33 

15 

ND 

9.6 

2.9 

9.0 

37 

128 

29% 













median 

29% 

04/15/2002 














Raw 

7.4 

ND 

17 

9.0 

30 

3.0 

ND 

4.5 

3.7 

8.2 

19 

46 

42% 

Pre-Ozone Eff. 

343 

5.2 

618 

88 

2021 

140 

2.6 

165 

36 

551 

894 



GAC/Sand Inf. 

159 

4.8 

235 

69 

713 

65 

2.4 

63 

29 

194 

353 

317 

111% 

GAC/Sand Eff. 

37 

ND 

72 

22 

101 

15 

ND 

19 

9.1 

28 

71 



GAC Inf. 

71 

ND 

137 

36 

286 

29 

ND 

37 

15 

78 

158 

553 

29% 

GAC Eff. 

31 

ND 

82 

23 

88 

13 

ND 

22 

9.5 

24 

68 

315 

22% 













median 

35% 

Formula 

CH 3 COO' 

CHjCHjCOO' 

HCOO' 

CHjCOCOO' 

CjO* 2 ' 


MW (gm/mole) 

59 

73 

45 

87 

88 

C portion (qm/mole) 

24 

36 

12 

36 

24 

C% of MW 

41% 

49% 

27% 

41% 

27% 


a Method detection limit (MDL) = 3 pg/L; reporting detection level (RDL) = 15 pg/L; value in italics is < RDL 
b ND = Not detected, value is < MDL 

C NR = Not reported; apparent problems with the results of this sample 


173 
































































Figure 3 


Formation and Removal of Carboxylic Acids at Plant 5 

(August 13, 2001) 


Acetate □ Propionate H Formate ■ Pyruvate □ Oxalate 


4000 

3500 

3000 

2500 

2000 














Conventional Train 




Super Pulsator Train 



— 

,, 


o> 

3 

;u 

o 

< 


>* 

o 1500 

si 

L- 

(0 

o 1000 


500 

0 


Raw 


Pre-Ozone GAC/Sand GAC/Sand GAC Influent GAC Effluent 

Effluent Influent Effluent 


Figure 4 

Seasonal Variation in Formation and Degradation 
of Oxalate at Plant 5 



Effluent 


174 






























































Ozonation resulted in a significant increase in the concentration of AOC (Table 11, 
Figure 5). (Note, one of the bacterial strains used in the AOC method [i.e., Spirillum NOX\ is 
used to estimate oxalate-carbon equivalents of the AOC [van der Kooij and Hijnen, 1984].) In 
August 2001, there was a significant reduction in the AOC on the GAC filter in the Super 
Pulsator train. (AOC was not sampled at the GAC/sand filter effluent in the conventional train, 
but based on carboxylic acid data [Figure 3], AOC should have been reduced in concentration.) 
In the other seasons, there was less AOC removal. The higher removal in August 2001 may 
have been due, in part, to the higher water temperature in the summer, which would have 
supported more biological activity. 


Figure 5 


Formation and Removal of AOC at Plant 5 (August 13, 2001) 

■ AOC-P17 □ AOC-NOX 



*AOC evaluated with two test bacteria: Pseudomonas fluorescens P-17 and Spirillum NOX 

Halogenated Organic and Other Nonhalogenated Organic DBPs. Tables 12 and 13 
(11/27/00), Tables 15 and 16 (2/26/01), Tables 18 and 19 (8/13/01), Tables 22 and 23 (10/22/01), 
and Tables 24 and 25 (4/15/02) show results for the halogenated organic DBPs that were 
analyzed at Metropolitan Water District of Southern California (MWDSC). Table 14 (11/27/00), 
Table 20 (8/13/01), and Table 26 (4/15/02) show results for additional target DBPs that were 
analyzed for at the University of North Carolina (UNC). Table 17 (2/26/01 [plant 6] and 
10/22/01 [plant 5]) shows results from broadscreen DBP analyses conducted at the U.S. 
Environmental Protection Agency (USEPA). Table 21 (8/13/01) and Table 27 (4/15/02) show 
results for halogenated furanones that were analyzed at UNC. 


175 











































Table 12. DBP results at Plant 5 (11/27/00) 


11/27/2000 

"mrlT 

Plant 5 b 

Compound 

mq/l 

Raw 

GAC/Sand Inf 

GAC Inf 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Halomethanes 










Chloromethane 

0.15 

ND° 



ND 

ND 


ND 


Bromomethane 

0.20 

ND 



ND 

ND 


ND 


Bromochloromethane 

0.14 

ND 



ND 

ND 


ND 


Dibromomethane 

0.11 

ND 



ND 

ND 


ND 


Chloroform d 

0.10 

0.8 

NR e 

NR 

12 

15 

NR 

48 

NR 

Bromodichloromethane d 

0.10 

0.3 

NR 

NR 

14 

16 

NR 

30 

NR 

Dibromochloromethane d 

0.12 

0.2 

NR 

NR 

13 

15 

NR 

16 

NR 

Bromoform d 

0.12 

ND 

NR 

NR 

2 

2 

NR 

2 

NR 

THM4 f 


1.3 

NR 

NR 

41 

48 

NR 

96 

NR 

Dichloroiodomethane 

0.25 

ND 

NR 

NR 

ND 

ND 

NR 

ND 

NR 

Bromochloroiodomethane 

3 

ND 

ND 

ND 

<3 9 

<3 

NR 

<1 h 

NR 

Dibromoiodomethane 

0.64 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

3 

ND 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

Carbon tetrachloride 

0.06 

ND 



ND 

ND 


ND 


Haloacetic acids 










Monochloroacetic acid d 

2 




3.5 

3.5 


3.4 


Monobromoacetic acid d 

1 




ND 

ND 


ND 


Dichloroacetic acid d 

1 




8.7 

9.8 


22 


Bromochloroacetic acid d 

1 




7.0 

7.7 


12 


Dibromoacetic acid d 

1 




2.2 

2.5 


4.9 


Trichloroacetic acid d 

1 




3.8 

5.3 


9.0 


Bromodichloroacetic acid 

1 




5.7 

7.0 


8.1 


Dibromochloroacetic acid 

1 




2.9 

3.4 


4.2 


Tribromoacetic acid 

2 




ND 

ND 


ND 


HAA5' 





18 

21 


39 


HAA9 J 





34 

39 


64 


DXAA k 





18 

20 


39 


TXAA 1 





12 

16 


21 


Haloacetonitriles 










Chloroacetonitrile 

0.10 

ND 

ND 

ND 

0.1 

0.2 

ND 

ND 

ND 

Bromoacetonitrile 

0.10 

ND 

0.2 

ND 

0.1 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.10 

ND 

ND 

ND 

1 

1 

2 

2 

2 

Bromochloroacetonitrile d 

0.10 

ND 

ND 

ND 

1 

1 

2 

2 

2 

Dibromoacetonitrile d 

0.10 

ND 

ND 

ND 

0.7 

0.7 

0.9 

0.9 

0.8 

T richloroacetonitrile d 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetaldehydes 










Dichloroacetaldehyde 

0.16 

ND 

ND 

ND 

1 

1 

1 

1 

1 

Brornochloroacetaldehyde m 
Chloral hydrate d 

0.20 

ND 

ND 

ND 

6 

7 

21 

27 

29 

T ribromoacetaldehyde 

0.10 

ND 

ND 

ND 

0.1 

0.1 

ND 

ND 

ND 


176 






























































Table 12 (continued) 


11/27/2000 

MRL d 

Plant 5 b 

Compound 

mq/l 

Raw 

GAC/Sand Inf 

GAC Inf 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloketones 










Chloropropanone 

0.10 

ND 

ND 

ND 

0.3 

0.2 

0.3 

0.2 

0.3 

1,1-Dichloropropanone 

0.10 

ND 

ND 

ND 

0.5 

0.4 

0.2 

0.2 

ND 

1,3-Dichloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

3 

ND 



ND 

ND 


ND 


1,1,1 -T richloropropanone d 

0.10 

ND 

ND 

ND 

4 

4 

8 

9 

8 

1,1,3-T richloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

3 

ND 



<3 

3 


<1 


1,1,1 -T ribromopropanone 

3 

ND 



ND 

ND 


ND 


1,1,3-T ribromopropanone 

3 

ND 



ND 

ND 


ND 


1,1,3,3-T etrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrabromopropanone 

0.10 

ND 

ND 

ND 

0.1 

0.1 

ND 

ND 

ND 

Halonitromethanes 










Bromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

3 

ND 



ND 

ND 


<3 


Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

0.1 

ND 

ND 

Chloropicrin 0 

0.10 

ND 

ND 

ND 

0.4 

0.4 

3 

2 

3 

Miscellaneous Compounds 










Methyl ethyl ketone 

1.90 

ND 



ND 

ND 


ND 


Methyl tertiary butyl ether 

0.16 

ND 



ND 

ND 


ND 


Benzyl chloride 

0.50 

ND 

ND 

ND 

ND 

ND 

NR 

ND 

NR 


a MRL = Minimum reporting level, which equals method detection limit (MDL) 
or lowest calibration standard or concentration of blank 

b Treatment plant sampled at (1) raw water, conventional train sampled at (2) GAC/sand influent, 

Super Pulsator train sampled at (3) GAC influent, (4) plant effluent, 

(5) DS at average detention time and (6) at maximum detention time, and 

(7) SDS testing of plant effluent held for average detention time and (8) held for maximum detention time. 


C ND = Not detected at or above MRL 

d DBP in the Information Collection Rule (ICR) (note: some utilities collected data for all 9 
haloacetic acids for the ICR, but monitoring for only 6 haloacetic acids was required) 

e NR = Not reported, due to interference problem on gas chromatograph or to problem with quality assurance 
f THM4 = Sum of 4 THMs (chloroform, bromodichloromethane, dibromochloromethane, bromoform) 


9 <3: Concentration less than MRL of 3 pg/L 

h <1: Concentration less than lowest calibration standard (i.e., 1 pg/L) 

'HAA5 = Sum of 5 haloacetic acids (monochloro-, monobromo-, dichloro-, dibromo-, trichloroacetic acid) 
j HAA9 = Sum of 9 haloacetic acids 

k DXAA = Sum of dihaloacetic acids (dichloro-, bromochloro-, dibromoacetic acid) 

'TXAA = Sum of trihaloacetic acids (trichloro-, bromodichloro-, dibromochoro-, tribromoacetic acid) 
m Brornochloroacetaldehyde and chloral hydrate co-eulte; result = sum of 2 DBPs 


177 








































Table 13. DBP results at Plant 6 (11/27/00) 


11/27/2000 

MRL* 

pg/L 

Plant 6 n 

Compound 

Raw 

Settled 

Filter Eff 

Clearwell Eff 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Halomethanes 











Chloromethane 

0.15 

ND C 


ND 


ND 

ND 


ND 


Bromomethane 

0.20 

ND 


ND 


ND 

ND 


ND 


Bromochloromethane 

0.14 

ND 


ND 


ND 

ND 


ND 


Dibromomethane 

0.11 

ND 


ND 


ND 

ND 


ND 


Chloroform d 

0.10 

0.3 

0.8 

4 

NR e 

8 

8 

NR 

10 

NR 

Bromodichloromethane d 

0.10 

0.3 

1 

4 

NR 

8 

8 

NR 

9 

NR 

Dibromochloromethane d 

0.12 

ND 

0.5 

2 

NR 

5 

5 

NR 

5 

NR 

Bromoform d 

0.12 

ND 

ND 

0.5 

NR 

1 

1 

NR 

1 

NR 

THM4 f 


0.6 

2 

11 

NR 

22 

22 

NR 

25 

NR 

Dichloroiodomethane 

0.25 

ND 

NR 

ND 

NR 

0.3 

0.3 

NR 

0.4 

NR 

Bromochloroiodomethane 

3 

ND 

NR 

ND 

NR 

<3 9 

<3 

NR 

<1 h 

NR 

Dibromoiodomethane 

0.64 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

0.1 

0.2 

Bromodiiodomethane 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

3 

ND 

NR 

ND 

NR 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 

ND 


ND 


ND 

ND 


ND 


Haloacetic acids 











Monochloroacetic acid d 

2 


2.0 

2.4 

2.6 

ND 

2.3 


2.2 


Monobromoacetic acid d 

1 


ND 

ND 

1.0 

ND 

ND 


ND 


Dichloroacetic acid d 

1 


11 

14 

16 

16 

17 


16 


Bromochloroacetic acid d 

1 


5.2 

7.8 

9.1 

9.3 

9.5 


9.4 


Dibromoacetic acid d 

1 


ND 

1.5 

2.0 

2.0 

2.1 


2.0 


Trichloroacetic acid d 

1 


ND 

2.7 

3.7 

3.5 

3.2 


3.6 


Bromodichloroacetic acid 

1 


ND 

1.7 

2.1 

2.0 

1.9 


2.0 


Dibromochloroacetic acid 

1 


ND 

1.0 

1.1 

1.0 

1.1 


1.1 


Tribromoacetic acid 

2 


ND 

ND 

ND 

ND 

ND 


ND 


HAA5' 



13 

20 

25 

22 

25 


24 


HAA9' 



18 

31 

38 

34 

37 


37 


DXAA k 



16 

23 

27 

28 

29 


28 


TXAA' 



ND 

5.4 

6.9 

6.5 

6.2 


6.7 


Halnarptnnitrilps 











Chloroacetonitrile 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.10 

ND 

0.2 

0.5 

0.7 

0.7 

0.8 

0.9 

0.8 

1 

Bromochloroacetonitrile d 

0.10 

ND 

0.1 

0.3 

0.4 

0.4 

0.4 

0.6 

0.5 

0.5 

Dibromoacetonitrile d 

0.10 

ND 

ND 

ND 

0.1 

0.1 

0.1 

0.1 

0.1 

0.1 

T richloroacetonitrile 0 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetaldehvdes 











Dichloroacetaldehyde 

0.16 

ND 

0.6 

1 

1 

2 

2 

5 

2 

2 

Brornochloroacetaldehyde m 

Chloral hydrate d 

0.20 

ND 

ND 

1 

2 

2 

2 

3 

2 

2 

T ribromoacetaldehyde 

0.10 

ND 

ND 

0.1 

ND 

ND | ND 

ND 

0.1 

0.1 


178 



























































Table 13 (continued) 


11/27/2000 

"mrI7 

mq/l 

Plant 6" 

Compound 

Raw 

Settled 

Filter Eff 

Clearwell Eff 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Haloketones 











Chloropropanone 

0.10 

ND 

0.4 

0.5 

0.6 

0.6 

0.6 

1 

0.8 

0.9 

1,1 -Dichloropropanone d 

0.10 

ND 

0.5 

0.9 

1 

1 

1 

2 

1 

2 

1,3-Dichloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

3 

ND 


ND 


ND 

ND 


ND 


1,1,1-Trichloropropanone d 

0.10 

ND 

0.1 

0.5 

0.5 

0.5 

0.4 

0.1 

0.4 

0.5 

1,1,3-T richloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

3 

ND 


<1 


<1 

<1 


<1 


1,1,1 -T ribromopropanone 

3 

ND 


ND 


ND 

ND 


ND 


1,1,3-T ribromopropanone 

3 

ND 


ND 


ND 

ND 


ND 


1,1,3,3-T etrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrabromopropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 











Bromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

3 

ND 


ND 


ND 

ND 


<1 


Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin d 

0.10 

ND 

ND 

ND 

0.2 

0.2 

0.3 

0.7 

0.4 

0.8 

Miscellaneous Compounds 











Methyl ethyl ketone 

1.90 

ND 


ND 


ND 

ND 


ND 


Methyl tertiary butyl ether 

0.16 

ND 


ND 


ND 

ND 


ND 


Benzyl chloride 

0.50 

ND 

NR 

ND 

NR 

ND 

ND 

NR 

ND 

NR 


"Treatment plant sampled at (1) raw water, (2) settled water, (3) filter effluent, (4) clearwell effluent, 

(5) plant effluent, (6) DS at average detention time and (7) at maximum detention time, and 

SDS testing of plant effluent (8) held for average detention time and (9) held for maximum detention time. 


Table 14. Additional target DBP results (ng/L) at plants 5 and 6 (11/27/00) 


11/27/2000 

Plant 5 a 

Plant 6 b 

Compound 

Raw 

OE1 

Comb FE 

PE 

DS/ave 

SDS/max 

Raw 

Settled 

FE 

PE 

DS/ave 

SDS/max 

Monochloroacetaldehyde 

0 

0 

0 

0.2 

0.1 

0.6 

0 

0.6 

0.7 

0.3 

0.4 

0.3 

Dichloroacetaldehyde 

0 

0 

0 

2.0 

1.9 

2.6 

0 

0.6 

1.0 

1.3 

1.8 

1.3 

Bromochloroacetaldehyde 

0 

0 

0 

2.2 

2.0 

2.3 

0 

0.7 

1.2 

1.8 

2.3 

1.8 

3,3-Dichloropropenoic acid 

0.2 

0.1 

0.1 

0.9 

1.3 

0.6 

0.1 

0.4 

0.5 

0.7 

0.9 

1.4 

Bromochloromethylacetate 

0 

0 

0 

0 

0 

0 

0 

0 

0 

1.1 

0 

0 

2,2-Dichloroacetamide 

0 

0 

0 

0 

0 

0 

0 

0 

0 

1.5 

1.2 

2.5 

TOX (fig/L as CF) 

36.9 


16.1 

205 

227 

245 

15.2 

88.8 

120 

146 

124 

148 

Cyanoformaldehyde 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

0.1 

<0.1 

<0.1 

<0.1 

<0.1 

5-Keto-l-hexanal 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

6-Hydroxy-2-hexanone 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

Dimethyglyoxal 

<0.4 

0.7 

3.2 

2.1 

2.1 

2.1 

<0.4 

1.1 

0.6 

1.7 

1.3 

1.8 

trans -2-Hexenal 

<0.1 

0.3 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 


a OEl= Raw-water ozone contactor effluent. Comb FE = combined filter effluent, PE = plant effluent 
b FE = Filter effluent, PE = plant effluent 


179 




































































Table 15. DBP results at plant 5 (2/26/01) 


2/26/2001 

MRL d 

mq/l 

Plant 5 b 

Compound 

Raw 

GAC/Sand Inf 

GAC Inf 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Halomethanes 










Chloromethane 

0.15 

ND C 



ND 

ND 


ND 


Bromomethane 

0.20 

ND 



ND 

ND 


ND 


Bromochloromethane 

0.14 

ND 



ND 

ND 


ND 


Dibromomethane 

0.11 

ND 



ND 

ND 


ND 


Chloroform d 

0.1 

0.1 

ND 

0.1 

3 

17 

15 

34 

41 

Bromodichloromethane d 

0.1 

ND 

ND 

ND 

8 

12 

12 

16 

14 

Dibromochloromethane d 

0.10 

ND 

ND 

ND 

6 

7 

7 

6 

5 

Bromoform d 

0.12 

ND 

ND 

ND 

0.6 

1 

ND 

0.6 

ND 

THM4 f 


0.1 

ND 

0.1 

18 

37 

34 

57 

60 

Dichloroiodomethane 

0.25 

ND 

NR e 

NR 

0.3 

0.3 

NR 

0.3 

NR 

Bromochloroiodomethane 

0.20 

ND 

NR 

NR 

ND 

ND 

NR 

ND 

NR 

Dibromoiodomethane 

0.48 

ND 

NR 

NR 

ND 

ND 

NR 

ND 

NR 

Chlorodiiodomethane 

0.51 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.56 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.54 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 

ND 



ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 










Monochloroacetic acid d 

2 




ND 

4.9 


5.4 


Monobromoacetic acid d 

1 




ND 

1.1 


ND 


Dichloroacetic acid d 

1 




9.8 

16 


20 


Bromochloroacetic acid d 

1 




5.0 

9.2 


7.4 


Dibromoacetic acid d 

1 




1.2 

2.8 


1.5 


Trichloroacetic acid d 

1 




4.8 

13 


8.5 


Bromodichloroacetic acid 

1 




4.8 

10 


5.1 


Dibromochloroacetic acid 

1 




2.2 

3.4 


1.9 


Tribromoacetic acid 

2 




ND 

ND 


ND 


HAA5 1 





16 

38 


35 


HAA9' 





28 

60 


50 


DXAA k 





16 

28 


29 


TXAA' 





12 

26 


16 


Haloacetnnitrilfis 










Chloroacetonitrile 

0.1 

ND 

ND 

ND 

0.1 

0.2 

0.2 

0.3 

0.3 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.10 

ND 

ND 

ND 

1 

1 

1 

2 

2 

Bromochloroacetonitrile d 

0.1 

ND 

ND 

ND 

0.8 

0.8 

0.8 

1 

0.8 

Dibromoacetonitrile d 

0.17 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

T richloroacetonitrile 0 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetaldehydes 










Dichloroacetaldehyde 

0.16 

ND 

ND 

0.2 

0.7 

0.5 

0.5 

0.7 

0.5 

Bromochloroacetaldehyde 

0.1 

ND 

ND 

ND 

0.4 

0.3 

0.2 

0.2 

0.1 

Chloral hydrate d 

0.1 

ND 

ND 

ND 

3 

5 

5 

9 

10 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


180 






























































Table 15 (continued) 


2/26/2001 

"mrlT 

mq/l 

Plant 5 b 

Compound 

Raw 

GAC/Sand Inf 

GAC Inf 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloketones 










Chloropropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dichioropropanone 

0.11 

ND 

ND 

ND 

0.5 

0.2 

0.2 

0.3 

0.2 

1,3-Dichloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

3 

ND 



ND 

ND 


ND 


1,3-Dibromopropanone 

3 

ND 



ND 

ND 


ND 


1,1,1 -T richloropropanone 

0.10 

ND 

ND 

ND 

3 

4 

4 

8 

6 

1,1,3-T richloropropanone 

0.11 

ND 

ND 

ND 

0.1 

ND 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

3 

ND 



A 

OJ 

CO 

<1 h 


<1 


1,1,1 -T ribromopropanone 

3 

ND 



ND 

ND 


ND 


1,1,3-T ribromopropanone 

3 

ND 



ND 

ND 


ND 


1,1,3,3-T etrachloropropanone 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-T etrachloropropanone 

3 

ND 



<1 

<1 


<1 


1,1,3,3-T etrabromopropanone 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 










Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

3 

ND 



<1 

<3 


<1 


Bromochloronitromethane 

3 

ND 



<3 

3 


<3 


Dibromonitromethane 

0.12 

ND 

ND 

ND 

0.2 

0.2 

0.2 

0.1 

0.1 

Chloropicrin 0 

0.1 

ND 

ND 

ND 

0.2 

1 

0.9 

0.9 

1 

Miscellaneous Compounds 










Methyl ethyl ketone 

1.90 

ND 



ND 

ND 


ND 


Methyl tertiary butyl ether 

0.16 

ND 



ND 

ND 


ND 


Benzyl chloride 

2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


181 









































Table 16. PBP results at plant 6 (2/26/01) 


2/26/2001 

MRL d 

Plant 6 n 


Compound 

pg/L 

Raw 

Settled 

Filter Eff 

Clearwell Eff 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Halomethanes 











Chloromethane 

0.15 

ND C 


ND 


ND 

ND 


ND 


Bromomethane 

0.20 

ND 


ND 


ND 

ND 


ND 


Bromochloromethane 

0.14 

ND 


ND 


ND 

ND 


ND 


Dibromomethane 

0.11 

ND 


ND 


ND 

ND 


ND 


Chloroform d 

0.1 

0.1 

0.2 

1 

1 

2 

5 

1 

2 

2 

Bromodichloromethane d 

0.1 

ND 

0.1 

0.8 

2 

2 

5 

4 

3 

3 

Dibromochloromethane d 

0.10 

ND 

ND 

0.2 

0.6 

0.4 

1 

1 

0.6 

0.6 

Bromoform d 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

THM4' 


0.1 

0.3 

2 

4 

4 

11 

6 

6 

6 

Dichloroiodomethane 

0.25 

ND 

NR e 

0.2 

NR 

0.3 

0.4 

NR 

0.3 

NR 

Bromochloroiodomethane 

0.20 

ND 

NR 

ND 

NR 

ND 

ND 

NR 

ND 

NR 

Dibromoiodomethane 

0.48 

ND 

NR 

ND 

NR 

ND 

ND 

NR 

ND 

NR 

Chlorodiiodomethane 

0.51 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.56 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.54 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 

ND 


ND 


ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 











Monochloroacetic acid d 

2 


ND 

ND 

2.0 

ND 

2.8 


ND 


Monobromoacetic acid d 

1 


ND 

ND 

1.2 

ND 

1.2 


ND 


Dichloroacetic acid d 

1 


10 

14 

17 

16 

22 


18 


Bromochloroacetic acid d 

1 


1.8 

3.2 

4.5 

4.3 

7.1 


4.1 


Dibromoacetic acid d 

1 


ND 

ND 

ND 

ND 

1.0 


ND 


Trichloroacetic acid d 

1 


ND 

2.4 

4.7 

3.8 

5.7 


3.1 


Bromodichloroacetic acid 

1 


ND 

ND 

1.5 

1.3 

2.0 


ND 


Dibromochloroacetic acid 

1 


ND 

ND 

ND 

ND 

ND 


ND 


Tribromoacetic acid 

2 


ND 

ND 

ND 

ND 

ND 


ND 


HAA5 1 



10 

16 

25 

20 

33 


21 


HAA9' 



12 

20 

31 

25 

42 


25 


DXAA k 



12 

17 

22 

20 

30 


22 


TXAA 1 



ND 

2.4 

6.2 

5.1 

7.7 


3.1 


Haloacetonitriles 











Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.10 

ND 

0.1 

0.2 

0.5 

0.3 

0.9 

0.6 

0.6 

0.7 

Bromochloroacetonitrile d 

0.1 

ND 

ND 

0.1 

0.2 

0.1 

0.3 

0.3 

0.2 

0.2 

Dibromoacetonitrile d 

0.17 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

T richloroacetonitrile 3 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetaldehydes 











Dichloroacetaldehyde 

0.16 

ND 

0.3 

0.5 

1 

0.8 

1 

1 

1 

2 

Bromochloroacetaldehyde 

0.1 

<0.1 

0.2 

0.3 

0.3 

0.4 

0.5 

0.8 

0.5 

0.5 

Chloral hydrate d 

0.1 

<0.1 

0.1 

0.4 

0.5 

0.4 

1 

0.5 

0.6 

0.6 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


182 
































































Table 16 (continued) 


2/26/2001 

MRL* 

mq/l 

Plant 6" 

Compound 

Raw 

Settled 

Filter Eff 

Clearwell Eff 

Plant Eff 

DS/Ave 

D S/M ax 

S DS/Ave 

SDS/Max 

Haloketones 











Chloropropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dichloropropanone d 

0.11 

ND 

0.4 

0.6 

1 

0.9 

2 

1 

1 

1 

1,3-Dichloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

3 

ND 


ND 


ND 

ND 


ND 


1,3-Dibromopropanone 

3 

ND 


ND 


ND 

ND 


ND 


1,1,1-Trichloropropanone d 

0.10 

ND 

ND 

0.3 

0.6 

0.4 

0.8 

0.3 

0.4 

0.4 

1,1,3-T richloropropanone 

0.11 

ND 

ND 

ND 

ND 

ND 

0.2 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

3 

ND 


<1 h 


<1 

<1 


<1 


1,1,1 -T ribromopropanone 

3 

ND 


ND 


ND 

ND 


ND 


1,1,3-T ribromopropanone 

3 

ND 


ND 


ND 

ND 


ND 


1,1,3,3-T etrachloropropanone 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-T etrachloropropanone 

3 

ND 


<1 


<1 

<1 


<1 


1,1,3,3-T etrabromopropanone 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 











Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

3 

ND 


ND 


ND 

ND 


ND 


Bromochloronitromethane 

3 

ND 


ND 


ND 

ND 


ND 


Dibromonitromethane 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin d 

0.1 

ND 

ND 

0.1 

0.3 

0.1 

0.4 

0.4 

0.4 

0.5 

Miscellaneous Compounds 











Methyl ethyl ketone 

1.90 

ND 


ND 


ND 

ND 


ND 


Methyl tertiary butyl ether 

0.16 

ND 


ND 


ND 

ND 


ND 


Benzyl chloride 

2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


183 










































Table 17. Occurrence of other DBPs a at plants 5 and 6 



Plant 6 (2/26/01) 

Plant 5 (10/22/01) 

Compound 

C10 2 

C10 2 + C1 2 /NH 2 C1 

o 3 

0 3 + Cl 2 

Halomethanes 

Bromodich!oromethane b 

X 

X 

X 

X 

Dibromochloromethane 

X 

X 

X 

X 

Bromoform 

X 

X 

X 

X 

Dichloroiodomethane 

X 

X 

- 

X 

Bromochloroiodomethane 

X 

X 

- 

- 

Haloacids 

Chloroacetic acid 

X 

X 

_ 

- 

Dichloroacetic acid 

X 

X 

X 

X 

Bromochloroacetic acid 

X 

X 

- 

- 

Dibromoacetic acid 

X 

X 

- 

- 

Bromodichloroacetic acid 

- 

X 

- 

- 

Trichloroacetic acid 

X 

X 

- 

- 

3,3-Dichloropropenoic acid 

X 

X 

- 

- 

Trichloropropenoic acid 

X 

X 

- 

- 

3,4,4-Trichloro-3-butenoic acid 

- 

- 

- 

X 

Haloacetonitriles 

Dichloroacetonitrile 

X 

X 

X 

X 

Bromochloroacetonitrile 

X 

X 

- 

X 

Dibromoacetonitrile 

X 

X 

- 

X 

Tribromoacetonitrile 

X 

X 

- 

- 

Haloaldehvdes 

Dichloroacetaldehyde 

X 

X 

_ 

. 

Trichloroacetaldehyde 

X 

X 

X 

X 

2-Bromo-2-methylpropanal 

X 

X 

X 

X 

*Iodobutanal 

X 

X 

- 

- 

Haloketones 

Chloropropanone 

X 

X 

_ 

_ 

1,1 -Dichloropropanone 

X 

X 

X 

X 

1 -Bromo-1 -chloropropanone 

X 

X 

- 

- 

1,1,1 -T richloropropanone 

X 

X 

X 

X 

1 -Bromo-1,1 -dichloropropanone 

- 

X 

- 

X 

1,1,3,3-Tetrachloropropanone 

X 

X 

- 

- 

1,1,1,3-Tetrachloropropanone 

- 

X 

- 

- 

1 -Bromo-1,3,3-trichloropropanone 

X 

X 

- 

- 

1 ,l-Dibromo-3,3-dichloropropanone 

X 

X 

- 

- 

Pentachloropropanone 

- 

X 

- 

X 

Halonitromethanes 

T richloronitromethane 


X 


X 

Miscellaneous Haloeenated DBPs 

Hexachlorocyclopentadiene 


X 



Dichloroacetic acid methyl ester 

X 

X 

- 

- 

Non-halogenated DBPs 

Glyoxal 

. 


X 

X 

Methyl glyoxal 

- 

- 

X 

X 

Hexanoic acid 

X 

- 

- 

- 

Decanoic acid 

X 

X 

- 

- 

Hexadecanoic acid 

- 

X 

- 

- 


a DBPs detected by broadscreen gas chromatography/mass spectrometry (GC/MS) technique 
b Compounds listed in italics were confirmed through the analysis of authentic standards; 
haloacids and non-halogenated carboxylic acids identified as their methyl esters. 


184 
























Table 18. DBP results at plant 5 (8/13/01) 


8/13/2001 

MRp 

mq/l 

Plant 5 b 

Compound 

Raw 

GAC/Sand 

GAC Inf 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Halomethanes 










Chloromethane 

0.2 

ND C 



ND 

ND 


ND 


Bromomethane 

0.2 

ND 



ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 



ND 

ND 


ND 


Dibromomethane 

0.5 

ND 



ND 

ND 


ND 


Chloroform d 

0.1 

ND 

ND 

ND 

9 

15 

20 

12 

25 

Bromodichloromethane d 

0.1 

ND 

ND 

ND 

11 

15 

17 

11 

18 

Dibromochloromethane d 

0.1 

ND 

ND 

ND 

5 

6 

6 

5 

6 

Bromoform d 

0.11 

ND 

ND 

ND 

0.5 

0.6 

0.7 

0.4 

0.5 

THM4 f 


ND 

ND 

ND 

26 

37 

44 

28 

50 

Dichloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromoiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 

ND 



ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 










Monochloroacetic acid d 

2 




ND 

2.5 


7.1 


Monobromoacetic acid d 

1 




ND 

ND 


1.2 


Dichloroacetic acid d 

1 




18 

21 


40 


Bromochloroacetic acid d 

1 




11 

12 


14 


Dibromoacetic acid d 

1 




4.2 

4.2 


4.4 


Trichloroacetic acid d 

1 




12 

16 


18 


Bromodichloroacetic acid 

1 




7.9 

8.6 


1.1 


Dibromochloroacetic acid 

1 




2.6 

2.8 


2.0 


Tribromoacetic acid 

2 




ND 

ND 


ND 


HAA5' 





34 

44 


71 


HAA9< 





56 

67 


88 


DXAA k 





33 

37 


58 


TXAA 1 





23 

27 


21 


Haloacetonitriles 










Chloroacetonitrile 

0.1 

ND 

ND 

ND 

0.2 

0.2 

0.2 

0.3 

0.3 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.10 

ND 

ND 

ND 

2 

2 

2 

3 

5 

Bromochloroacetonitrile d 

0.1 

ND 

ND 

ND 

1 

1 

1 

1 

0.8 

Dibromoacetonitrile d 

0.14 

ND 

ND 

ND 

0.8 

0.9 

0.7 

0.3 

0.2 

T richloroacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 



ND 

ND 



ND 

Dibromochloroacetonitrile 

0.5 

ND 



ND 

ND 



ND 

T ribromoacetonitrile 

0.5 

ND 



ND 

ND 



ND 

Haloacetaldehydes 










Dichloroacetaldehyde 

0.1 

2° 

0.4° 

ND 

0.8° 

1° 

0.8° 

4° 

1° 

Bromochloroacetaldehyde 

0.5 

1° 

ND 

ND 

ND 

ND 

ND 

2 

ND 

Chloral hydrate d 

0.1 

2° 

0.1° 

ND 

11° 

15° 

18° 

17° 

26° 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


“Quality control problems with haloacetaldehydes 


185 



































































Table 18 (continued) 


8/13/2001 

MRL 3 

Rant 5 b 

Compound 

M9/L 

Raw 

GAC/Sand 

GAC Inf 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloketones 










Chloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dichloropropanone d 

0.10 

ND 

ND 

ND 

0.6 

0.5 

0.2 

0.3 

0.2 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T richloropropanone 

0.1 

ND 

ND 

ND 

5 

5 

2 

6 

5 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T ribromopropanone 

0.29 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR e 

1,1,3-T ribromopropanone 

0.14 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

1,1,3,3-Tetrachloropropanone 

0.5 

ND 



ND 

ND 


ND 


1,1,1,3-Tetrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrabromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 










Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

ND 

ND 

ND 

0.7 

0.9 

0.8 

0.1 

0.5 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

0.2 

0.2 

0.2 

ND 

0.1 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

0.1 

ND 

ND 

ND 

Chloropicrin d 

0.1 

ND 

ND 

ND 

0.4 

0.6 

0.7 

0.6 

1 

Bromodichloronitromethane 

0.5 

ND 



0.8 

1 



ND 

Dibromochloronitromethane 

0.5 

ND 



0.8 

0.7 



0.8 

Bromopicrin 

2.0 

ND 



ND 

ND 



ND 

Miscellaneous Compounds 










Methyl ethyl ketone 

0.5 

7 



2 

1 


3 


Methyl tertiary butyl ether 

0.2 

0.4 



0.3 

0.4 


1 


1,1,2,2-Tetrabromo-2-chloroethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Benzyl chloride 

0.25 

ND 

NR 

NR 

ND 

ND 

NR 

ND 

NR 


186 














































Table 19. DBP results at plant 6 (8/13/01) 


8/13/2001 

MRL 3 

Plant 6 n 

Compound 

Mg/L 

Raw 

Settled 

Filt Eff 

Clearwell 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Halomethanes 











Chloromethane 

0.2 

ND C 


ND 


ND 

ND 


ND 


Bromomethane 

0.2 

ND 


ND 


ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 


ND 


ND 

ND 


ND 


Dibromomethane 

0.5 

ND 


ND 


ND 

ND 


ND 


Chloroform 6 

0.1 

ND 

0.2 

10 

18 

17 

14 

9 

NR e 

18 

Bromodichloromethane 6 

0.1 

ND 

0.1 

5 

8 

8 

8 

8 

6 

11 

Dibromochloromethane 6 

0.1 

ND 

ND 

0.9 

2 

1 

2 

2 

1 

2 

Bromoform 6 

0.11 

ND 

ND 

ND 

ND 

ND 

ND 

0.1 

ND 

0.1 

THM4 f 

0 

ND 

0.3 

16 

28 

26 

24 

19 

NR 

31 

Dichloroiodomethane 

0.5 

ND 

ND 

0.8 

0.5 

0.9 

0.5 

ND 

0.5 

ND 

Bromochloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromoiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 

ND 


ND 


ND 

ND 


ND 


Tribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 











Monochloroacetic acid 6 

2 


ND 

ND 

6.3 

6.2 

5.3 


4.5 


Monobromoacetic acid 6 

1 


ND 

3.7 

ND 

ND 

3.5 


ND 


Dichloroacetic acid 6 

1 


4.8 

29 

38 

40 

40 


48 


Bromochloroacetic acid 6 

1 


1.2 

8.2 

11 

11 

12 


14 


Dibromoacetic acid 6 

1 


ND 

ND 

1.2 

ND 

1.7 


1.9 


Trichloroacetic acid 6 

1 


ND 

20 

21 

22 

19 


25 


Bromodichloroacetic acid 

1 


ND 

7.5 

7.9 

8.0 

8.1 


10 


Dibromochloroacetic acid 

1 


ND 

ND 

1.5 

1.2 

1.3 


1.5 


Tribromoacetic acid 

2 


ND 

ND 

ND 

ND 

ND 


ND 


HAA5' 



5 

53 

67 

68 

70 


79 


HAA9 1 



6 

68 

87 

88 

91 


105 


DXAA k 



6 

37 

50 

51 

54 


64 


TXAA 1 



ND 

28 

35 

31 

28 


37 


Haloacetonitriles 











Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile 6 

0.10 

ND 

0.2 

2 

2 

2 

2 

2 

3 

3 

Bromochloroacetonitrile 6 

0.1 

ND 

ND 

0.3 

0.5 

0.5 

0.6 

0.7 

0.4 

0.7 

Dibromoacetonitrile 6 

0.14 

ND 

ND 

ND 

ND 

ND 

0.2 

0.2 

0.1 

0.1 

T richloroacetonitrile 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 


ND 


ND 




ND 

Dibromochloroacetonitrile 

0.5 

ND 


ND 


ND 




ND 

T ribromoacetonitrile 

0.5 

ND 


ND 


ND 




ND 

Halnar.ataldehydes 











Dichloroacetaldehyde 

0.1 

2° 

ND 

ND 

ND 

ND 

ND 

ND 

6° 

3° 

Bromochloroacetaldehyde 

0.5 

0.7° 

ND 

0.8° 

ND 

ND 

ND 

ND 

2 

0.6 

Chloral hydrate 6 

0.1 

1° 

ND 

3° 

4° 

4° 

4° 

3° 

10° 

6° 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


“Quality control problems with haloacetaldehydes 


187 



































































Table 19 (continued) 


8/13/2001 

MRL 3 

Mg/L 

Plant 6 n 

Compound 

Raw 

Settled 

Filt Eff 

Clearwell 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Haloketones 











Chloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dichloropropanone d 

0.10 

ND 

0.7 

1 

0.7 

0.9 

2 

1 

2 

2 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T richloropropanone d 

0.1 

ND 

ND 

2 

2 

2 

1 

0.3 

0.5 

0.3 

1,1,3-Trichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T ribromopropanone 

0.29 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

1,1,3-T ribromopropanone 

0.14 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

1,1,3,3-Tetrachloropropanone 

0.5 

ND 


ND 


ND 

ND 


ND 


1,1,1,3-Tetrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrabromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 











Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

ND 

ND 

ND 

ND 

0.1 

ND 

ND 

0.1 

0.1 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin d 

0.1 

ND 

ND 

0.1 

0.2 

0.2 

0.3 

0.3 

0.3 

0.9 

Bromodichloronitromethane 

0.5 

ND 


ND 


ND 




ND 

Dibromochloronitromethane 

0.5 

ND 


ND 


ND 




ND 

Bromopicrin 

2.0 

ND 


ND 


ND 




ND 

Miscellaneous Compounds 











Methyl ethyl ketone 

0.5 

3 


4 


2 

1 


0.5 


Methyl tertiary butyl ether 

0.2 

0.3 


0.3 


0.5 

ND 


0.5 


1,1,2,2-T etrabromo-2-chloroethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Benzyl chloride 

0.25 

ND 

NR 

ND 

NR 

ND 

ND 

NR 

ND 

NR 


188 













































Table 20. Additional target DBP results (yig/L) at plants 5 and 6 (8/13/01) 


8/13/2001 

Plant 5 a 

Plant 6 

Compound 

Raw 

OE1 

GAC FE 

PE 

DS/ave 

SD S/max 

Raw 

Settled 

FE 

PE 

DS/ave 

SDS/max 

Monochloroacetaldehyde 

0 

0 

0 

0.1 

0.2 

0.3 

0 

0.3 

0.2 

0.1 

0.1 

0.1 

Dichloroacetaldehyde 

0 

0 

0 

2.1 

1.8 

5.1 

0 

0.5 

2.5 

3.5 

2.8 

4.2 

Bromochloroacetaldehyde 

0 

0 

0 

0.8 

1.1 

1.5 

0 

0 

0.4 

0.6 

1.0 

1.2 

3,3-Dichloropropenoic acid 

0 

0 

0 

0 

0 

4.4 

0 

0 

2.5 

4.7 

4.8 

5.5 

Bromochloromethylacetate 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

2,2-Dichloroacetamide 

0 

0 

0 

0 

0 

0 

0 

0 

0 

5.6 

4.1 

3.9 

TOX (pg/L as Cl") 

10.5 


11.5 

284 

257 

327 

12.7 

52.9 

203 

245 

238 

241 

Cyanoformaldehyde 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 


<0.1 

<0.1 

<0.1 

<0.1 

5-Keto-l-hexanal 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

6-Hydroxy-2-hexanone 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

Dimethyglyoxal 

<0.4 

2.4 

0.8 

1.8 

1.2 

1.9 

<0.4 

1.6 

0.5 

1.2 

1.4 

1.6 

trans -2-Hexenal 

<0.1 


<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 


a GAC FE = GAC filter effluent 


Table 21. Halogenated furanone results (ng/L) at plants 5 and 6 (8/13/01) 


8/13/2001 

Plant 5 

Plant 6 

Compound 

GAC FE 

PE 

DS/ave 

Raw 

Settled 

FE 

PE 

DS/ave 

MX 

<0.04 

<0.04 

<0.04 

<0.04 

<0.04 

<0.04 

0.31 

0.30 

ZMX 

<0.04 

<0.04 

<0.04 

<0.04 

<0.04 

<0.04 

<0.04 

<0.04 

EMX 

<0.04 

<0.04 

<0.04 

<0.04 

<0.04 

0.23 

<0.04 

0.12 

Mucochloric acid (ring) 

<0.04 

<0.04 

<0.04 

<0.04 

<0.04 

<0.04 

<0.04 

<0.04 

Mucochloric acid (open) 

<0.04 

<0.04 

<0.04 

<0.04 

<0.04 

<0.04 

<0.04 

<0.04 


189 












































Table 22. DBP results at plant 5 (10/22/01) 


10/22/2001 

MRL d 

Plant 5 b 


Compound 

MQ/L 

Raw 

GAC/Sand 

GAC Inf 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Halomethanes 










Chloromethane 

0.2 

ND C 



ND 

ND 


ND 


Bromomethane 

0.2 

ND 



ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 



ND 

ND 


ND 


Dibromomethane 

0.5 

ND 



ND 

ND 


ND 


Chloroform d 

0.5 

ND 

ND 

ND 

10 

34 

NR e 

58 

60 

Bromodichloromethane d 

0.1 

ND 

ND 

ND 

19 

31 

NR 

30 

30 

Dibromochloromethane d 

0.1 

ND 

ND 

ND 

12 

19 

20 

14 

12 

Bromoform d 

0.1 

ND 

ND 

ND 

2 

2 

1 

2 

2 

THM4 f 


ND 

ND 

ND 

43 

86 

NR 

104 

104 

Dichloroiodomethane 

0.5 

ND 

ND 

ND 

0.5 

<0.5 P 

NR 

ND 

ND 

Bromochloroiodomethane 

0.5 

ND 

NR 

NR 

ND 

ND 

NR 

ND 

NR 

Dibromoiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1-0.5 q 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

1.0 

ND 

NR 

NR 

ND 

ND 

NR 

ND 

NR 

Carbon tetrachloride 

0.2 

ND 



ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 










Monochloroacetic acid d 

2 




ND 

ND 


4.1 


Monobromoacetic acid d 

1 




ND 

ND 


1.2 


Dichloroacetic acid d 

1 




4.5 

5.9 


28 


Bromochloroacetic acid d 

1 




4.2 

4.9 


19 


Dibromoacetic acid d 

1 




2.5 

2.1 


5.2 


Trichloroacetic acid d 

1 




2.7 

6.4 


9.4 


Bromodichloroacetic acid 

1 




3.8 

6.2 


8.3 


Dibromochloroacetic acid 

1 




2.0 

2.5 


3.0 


Tribromoacetic acid 

2 




ND 

ND 


ND 


HAA5' 





10 

14 


48 


HAA9 j 





20 

28 


78 


DXAA k 





11 

13 


52 


TXAA' 





8.5 

15 


21 


Halnanetonitrilfis 










Chloroacetonitrile 

0.1 

ND 

ND 

ND 

0.2 

0.4 

ND 

0.4 

0.5 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.1 

ND 

ND 

ND 

1 

4 

4 

2 

3 

Bromochloroacetonitrile d 

0.1 

ND 

ND 

ND 

1 

2 

2 

2 

1 

Dibromoacetonitrile d 

0.1 

0.2 

ND 

ND 

0.9 

1 

0.7 

1 

0.6 

T richloroacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 



ND 

ND 



ND 

Dibromochloroacetonitrile 

0.5 

ND 



ND 

ND 



ND 

T ribromoacetonitrile 

0.9 

ND 



ND 

ND 



ND 

Haloacetaldehydes 










Dichloroacetaldehyde 

1.1 

0.4 

ND 

0.2 

1 

2 

2 

4 

3 

Bromochloroacetaldehyde 

0.5 

ND 

ND 

0.1 

0.5 

0.2 

1 

ND 

ND 

Chloral hydrate d 

0.1 

1 

ND 

0.4 

3 

8 

8 

13 

22 

T ribromoacetaldehyde 

0.1 

ND 

ND 

0.6 

ND 

ND 

ND 

ND 

ND 


190 



































































Table 22 (continued) 


10/22/2001 

"mrlT" 

Plant 5 b 

Compound 

mq/l 

Raw 

GAC/Sand 

GAC Inf 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Haloketones 










Chloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dichloropropanone d 

0.10 

ND 

ND 

ND 

0.7 

0.8 

0.7 

0.5 

0.2 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1-Trichloropropanone d 

0.1 

ND 

ND 

ND 

4 

5 

4 

4 

3 

1,1,3-Trichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

0.1 

ND 

ND 

ND 

0.4 

ND 

ND 

ND 

ND 

1,1,1 -T ribromopropanone 

0.1-0.3 q 

ND 

ND 

0.1 

ND 

ND 

ND 

ND 

ND 

1,1,3-T ribromopropanone 

0.1-0.7 q 

ND 

ND 

0.1 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrachloropropanone 

2.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

1,1,1,3-T etrachloropropanone 

0.10 

ND 

ND 

0.2 

0.1 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrabromopropanone 

0.5-2 q 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 










Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

0.1 

0.5 

Dichloronitromethane 

0.1 

ND 

ND 

ND 

0.3 

1 

1 

2 

2 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

0.4 

0.5 

0.5 

0.3 

0.2 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

0.6 

0.5 

0.4 

0.2 

0.1 

Chloropicrin d 

0.1 

ND 

ND 

ND 

0.3 

2 

2 

1 

NR 

Bromodichloronitromethane 

0.5 

ND 



ND 

ND 



1 

Dibromochloronitromethane 

0.5-2 r 

ND 



ND 

ND 



1 

Bromopicrin 

0.5 

ND 



2 

2 



ND 

Miscellaneous Compounds 










Methyl ethyl ketone 

0.5 

0.6 



ND 

ND 


ND 


Methyl tertiary butyl ether 

0.2 

ND 



ND 

ND 


ND 


1,1,2,2-Tetrabromo-2-chloroethane 

0.5-2 q 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Benzyl chloride 

0.25 

ND 

NR 

NR 

ND 

ND 

NR 

ND 

NR 


p <0.5 = Detected by GC/MS below its MRL of 0.5 |jg/L; 
quality assurance problem with gas chromatograph method 
q Higher MRL for SDS samples 
r Lower MRL for SDS samples 


191 










































Table 23. DBP results at plant 6 (10/22/01) 


10/22/2001 

MRL d 

Plant 6 n 

Compound 

mq/l 

Raw 

Settled 

Filt Eff 

Clearwell 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Halomethanes 











Chloromethane 

0.2 

ND C 


ND 


ND 

ND 


ND 


Bromomethane 

0.2 

ND 


ND 


ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 


ND 


ND 

ND 


ND 


Dibromomethane 

0.5 

ND 


ND 


ND 

ND 


ND 


Chloroform d 

0.5 

0.5 

0.6 

13 

NR e 

18 

24 

NR 

17 

22 

Bromodichloromethane d 

0.1 

0.1 

0.2 

12 

NR 

21 

24 

NR 

19 

26 

Dibromochloromethane d 

0.1 

ND 

ND 

4 

6 

7 

8 

NR 

8 

6 

Bromoform d 

0.1 

ND 

ND 

0.4 

0.5 

0.5 

0.5 

0.5 

0.6 

0.8 

THM4 f 


0.6 

0.8 

29 

NR 

47 

57 

NR 

45 

55 

Dichloroiodomethane 

0.5 

ND 

0.5 

3 

2 

3 

4 

NR 

3 

2 

Bromochloroiodomethane 

0.5 

ND 

NR 

ND 

NR 

<0.5 P 

<0.5 

NR 

<0.5 

NR 

Dibromoiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1-0.5 q 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

1.0 

ND 

NR 

ND 

NR 

ND 

ND 

NR 

ND 

NR 

Carbon tetrachloride 

0.2 

ND 


ND 


ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 











Monochloroacetic acid d 

2 


ND 

ND 

2.4 

2.2 

2.6 


3.0 


Monobromoacetic acid d 

1 


ND 

ND 

ND 

ND 

ND 


ND 


Dichloroacetic acid d 

1 


2.8 

9.7 

13 

12 

14 


23 


Bromochloroacetic acid d 

1 


1.3 

4.7 

6.6 

6.3 

7.2 


11 


Dibromoacetic acid d 

1 


ND 

1.6 

2.2 

2.0 

2.2 


3.1 


Trichloroacetic acid d 

1 


ND 

4.6 

7.4 

6.5 

6.9 


10 


Bromodichloroacetic acid 

1 


ND 

3.7 

4.8 

4.5 

4.5 


6.2 


Dibromochloroacetic acid 

1 


ND 

2.2 

2.3 

2.1 

2.0 


2.0 


Tribromoacetic acid 

2 


ND 

ND 

ND 

ND 

ND 


ND 


HAA5' 



2.8 

16 

25 

23 

26 


39 


HAA9' 



4.1 

27 

39 

36 

39 


58 


DXAA k 



4.1 

16 

22 

20 

23 


37 


TXAA' 



ND 

11 

15 

13 

13 


18 


Haloacetonitriles 











Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

0.4 

ND 

0.4 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.1 

ND 

0.1 

1 

2 

2 

3 

NR 

3 

4 

Bromochloroacetonitrile d 

0.1 

ND 

ND 

0.6 

0.9 

1 

1 

NR 

1 

2 

Dibromoacetonitrile d 

0.1 

ND 

ND 

0.2 

0.3 

0.4 

0.4 

NR 

0.4 

0.7 

T richloroacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 


ND 


ND 




ND 

Dibromochloroacetonitrile 

0.5 

ND 


ND 


ND 




0.5 

T ribromoacetonitrile 

0.9 

ND 


ND 


ND 




ND 

Halnar.otaldfihydfis 











Dichloroacetaldehyde 

1.1 

0.4 

ND 

2 

2 

2 

2 

8 

12 

12 

Bromochloroacetaldehyde 

0.5 

ND 

ND 

0.4 

0.5 

0.5 

0.7 

0.8 

2 

3 

Chloral hydrate d 

0.1 

ND 

ND 

ND 

3 

2 

3 

2 

6 

6 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

0.9 

ND 

1 


192 


































































Table 23 (continued) 


10/22/2001 

MRL a 

mq/l 

Plant 6 n 

Compound 

Raw 

Settled 

Filt Eff 

Clearwell 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Haloketones 











Chloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

0.1 

0.2 

ND 

ND 

1,1 -Dichloropropanone d 

0.10 

ND 

ND 

1 

0.9 

1 

2 

2 

2 

NR 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

0.1 

1,1-Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1-Trichloropropanone d 

0.1 

0.1 

ND 

2 

2 

2 

2 

NR 

2 

2 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

0.1 

ND 

ND 

0.4 

0.5 

0.4 

ND 

ND 

ND 

ND 

1,1,1 -T ribromopropanone 

0.1-0.3 q 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-T ribromopropanone 

0.1-0.7 q 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrachloropropanone 

2.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

1,1,1,3-T etrachloropropanone 

0.10 

ND 

ND 

0.1 

0.2 

0.1 

ND 

0.4 

ND 

0.5 

1,1,3,3-Tetrabromopropanone 

0.5-2 q 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 











Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

0.2 

ND 

0.2 

0.3 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin d 

0.1 

ND 

ND 

0.2 

0.2 

0.2 

0.4 

0.5 

0.6 

0.9 

Bromodichloronitromethane 

0.5 

ND 


ND 


ND 




0.8 

Dibromochloronitromethane 

0.5-2 r 

ND 


ND 


ND 




0.5 

Bromopicrin 

0.5 

ND 


ND 


ND 




ND 

Miscellaneous Compounds 











Methyl ethyl ketone 

0.5 

0.7 


ND 


ND 

0.6 


ND 


Methyl tertiary butyl ether 

0.2 

ND 


ND 


ND 

ND 


ND 


1,1,2,2-Tetrabromo-2-chloroethane 

0.5-2 q 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Benzyl chloride 

0.25 

ND 

NR 

ND 

NR 

ND 

ND 

NR 

ND 

NR 


193 













































Table 24. DBP results at plant 5 (4/15/02) 


4/15/2002 

MRL 3 

Plant 5 b 

Compound 

mq/l 

Raw 

GAC/Sand 

GAC Inf 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Halomethanes 










Chloromethane 

0.2 

ND C 



ND 

ND 


ND 


Bromomethane 

0.2 

ND 



ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 



ND 

ND 


ND 


Dibromomethane 

0.5 

ND 



ND 

ND 


ND 


Chloroform d 

0.2 

ND 

ND 

ND 

11 

26 

NR e 

49 

NR 

Bromodichloromethane d 

0.2 

ND 

ND 

ND 

14 

17 

NR 

26 

NR 

Dibromochloromethane d 

0.2 

ND 

ND 

ND 

7 

8 

NR 

7 

NR 

Bromoform d 

0.1 

ND 

ND 

ND 

0.9 

0.9 

0.7 

1 

1 

THM4 f 


ND 

ND 

ND 

33 

52 

NR 

83 

NR 

Dichloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloroiodomethane 

0.5 

ND 

NR 

NR 

ND 

ND 

NR 

ND 

NR 

Dibromoiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 

ND 



ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

NR 

NR 

ND 

ND 

NR 

ND 

NR 

Haloacetic adds 










Monochloroacetic acid d 

2 




2.2 

3.6 


6.2 


Monobromoacetic acid d 

1 




ND 

ND 


1.1 


Dichloroacetic acid d 

1 




12 

17 


26 


Bromochloroacetic acid d 

1 




5.3 

6.3 


6.4 


Dibromoacetic acid d 

1 




1.9 

1.9 


2.4 


Trichloroacetic acid d 

1 




6.9 

11 


9.2 


Bromodichloroacetic acid 

1 




7.3 

7.7 


7.1 


Dibromochloroacetic acid 

1 




2.1 

2.1 


2.0 


Tribromoacetic acid 

2 




ND 

ND 


ND 


HAA5 1 





23 

34 


45 


HAA9 j 





38 

50 


60 


DXAA k 





19 

25 


35 


TXAA 1 





16 

21 


18 


Haloacetonitriles 










Chloroacetonitrile 

0.1 

ND 

ND 

ND 

0.4 

0.3 

0.5 

0.8 

0.6 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.1 

ND 

ND 

ND 

NR 

1 

NR 

5 

NR 

Bromochloroacetonitrile d 

0.1 

ND 

ND 

ND 

1 

1 

0.8 

2 

1 

Dibromoacetonitrile d 

0.1 

ND 

ND 

ND 

0.4 

0.4 

0.4 

0.6 

0.6 

T richloroacetonitrile d 

0.5 

ND 

NR 

NR 

ND 

ND 

NR 

ND 

NR 

Bromodichloroacetonitrile 

0.5 

ND 



ND 

ND 



ND 

Dibromochloroacetonitrile 

0.5 

ND 



ND 

ND 



ND 

T ribromoacetonitrile 

0.96 

ND 



ND 

ND 



ND 

Haloacetaldehydes 










Dichloroacetaldehyde 

0.5 

ND 

ND 

0.5 

2 

2 

3 

4 

4 

Bromochloroacetaldehyde 

0.5 

ND 

ND 

ND 

0.5 

ND 

ND 

0.7 

0.6 

Chloral hydrate d 

0.1 

ND 

0.1 

0.3 

6 

6 

13 

22 

18 

T ribromoacetaldehyde 

0.1 

ND 

ND 

0.3 

ND 

ND 

ND 

ND 

ND 


194 
































































Table 24 (continued) 


4/15/2002 

MRL 3 

mq/l 

Plant 5 b 

Compound 

Raw 

GAC/Sand 

GAC Inf 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloketones 










Chloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dichloropropanone d 

1.0 

ND 

ND 

ND 

<1 s 

1 

NR 

ND 

NR 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T richloropropanone d 

0.5 

ND 

ND 

ND 

4 

8 

NR 

13 

NR 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

0.3 

ND 

NR 

NR 

0.4 

0.4 

NR 

ND 

NR 

1,1,1 -T ribromopropanone 

>5 

ND 

NR 

NR 

ND 

ND 

NR 

ND 

NR 

1,1,3-T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrachloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-Tetrachloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 










Chloronitromethane 

0.2 

ND 



0.6 

2 




Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

ND 

ND 

ND 

0.4 

0.5 

0.7 

0.7 

0.3 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

0.3 

ND 

Dibromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin d 

0.1 

ND 

ND 

ND 

1 

1 

3 

3 

3 

Bromodichloronitromethane 

0.5 

ND 



ND 

ND 



ND 

Dibromochloronitromethane 

2 

ND 



ND 

ND 



ND 

Bromopicrin 

0.5 

ND 



ND 

ND 



ND 

Miscellaneous Compounds 










Methyl ethyl ketone 

0.5 

0.7 



0.8 

0.7 


0.7 


Methyl tertiary butyl ether 

0.2 

ND 



ND 

ND 


ND 


1,1,2,2-T etrabromo-2-chloroethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Benzyl chloride 

0.25 

ND 

NR 

NR 

ND 

ND 

NR 

ND 

NR 


S <1 = Detected by GC/MS below its MRL of 1.0 pg/L; 
quality assurance problem with gas chromatograph method 


195 












































Table 25. DBP results at plant 6 (4/15/02) 


4/15/2002 

MRL* 

Plant 6 n 

Compound 

mq/l 

Raw 

Settled 

Filt Eff 

Clearwell 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Halomethanes 











Chloromethane 

0.2 

ND C 


ND 


0.2 

ND 


ND 


Bromomethane 

0.2 

ND 


ND 


ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 


ND 


ND 

ND 


ND 


Dibromomethane 

0.5 

ND 


ND 


ND 

ND 


ND 


Chloroform d 

0.2 

ND 

ND 

8 

NR e 

13 

19 

NR 

13 

18 

Bromodichloromethane d 

0.2 

ND 

0.4 

6 

NR 

10 

10 

NR 

11 

10 

Dibromochloromethane d 

0.2 

ND 

ND 

2 

NR 

3 

2 

NR 

3 

3 

Bromoform d 

0.1 

ND 

ND 

0.4 

0.4 

0.4 

0.2 

ND 

0.4 

0.5 

THM4 f 


ND 

0.4 

16 

NR 

26 

31 

NR 

27 

32 

Dichloroiodomethane 

0.5 

ND 

ND 

1 

NR 

1 

1 

ND 

0.7 

0.5 

Bromochloroiodomethane 

0.5 

ND 

NR 

<1 s 

NR 

<1 

<1 

NR 

<1 

ND 

Dibromoiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 

ND 


ND 


ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

NR 

ND 

NR 

ND 

ND 

NR 

ND 

ND 

Haloacetic acids 











Monochloroacetic acid d 

2 

ND 

ND 

2.3 

2.4 

2.5 

2.8 


3.3 


Monobromoacetic acid d 

1 

ND 

ND 

ND 

ND 

ND 

ND 


ND 


Dichloroacetic acid d 

1 

ND 

5.2 

16 

21 

22 

27 


27 


Bromochloroacetic acid d 

1 

ND 

ND 

5.0 

5.8 

8.3 

5.5 


6.7 


Dibromoacetic acid d 

1 

ND 

ND 

ND 

1.2 

1.2 

ND 


1.6 


Trichloroacetic acid d 

1 

ND 

ND 

5.0 

7.0 

6.7 

8.6 


7.2 


Bromodichloroacetic acid 

1 

ND 

ND 

3.1 

4.0 

4.0 

3.4 


4.0 


Dibromochloroacetic acid 

1 

ND 

ND 

1.2 

3.2 

3.5 

2.2 


1.1 


Tribromoacetic acid 

2 

ND 

ND 

ND 

ND 

ND 

ND 


ND 


HAA5' 


ND 

5.2 

23 

32 

32 

38 


39 


HAA9 J 


ND 

5.2 

33 

45 

48 

50 


51 


DXAA k 


ND 

5.2 

21 

28 

32 

33 


35 


TXAA 1 


ND 

ND 

9.3 

14 

14 

14 


12 


Haloacetonitriles 











Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

0.1 

0.2 

ND 

0.2 

0.2 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.1 

ND 

NR 

0.7 

NR 

1 

1 

NR 

4 

2 

Bromochloroacetonitrile d 

0.1 

ND 

ND 

0.4 

ND 

0.6 

0.6 

ND 

0.9 

1 

Dibromoacetonitrile d 

0.1 

ND 

ND 

ND 

0.2 

0.1 

<0.5 P 

ND 

0.2 

0.2 

T richloroacetonitrile d 

0.5 

ND 

NR 

ND 

NR 

ND 

ND 

NR 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 


ND 


ND 




ND 

Dibromochloroacetonitrile 

0.5 

ND 


ND 


ND 




ND 

T ribromoacetonitrile 

0.96 

ND 


ND 


ND 




ND 

Haloacetaldeh^des 











Dichloroacetaldehyde 

0.5 

ND 

0.5 

5 

3 

2 

4 

6 

5 

6 

Bromochloroacetaldehyde 

0.5 

ND 

ND 

1 

0.6 

ND 

ND 

ND 

0.7 

0.8 

Chloral hydrate d 

0.1 

1 

0.2 

2 

3 

2 

4 

4 

4 

4 

T ribromoacetaldehyde 

0.1 

ND 

ND 

0.9 

ND 

ND 

ND 

ND 

ND 

ND 


196 




































































Table 25 (continued) 


4/15/2002 

MRL 3 

pg/L 

Plant 6 n 

Compound 

Raw 

Settled 

Filt Eff 

Clearwell 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Haloketones 











Chloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dichloropropanone d 

1.0 

ND 

NR 

2 

NR 

2 

3 

NR 

2 

3 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T richloropropanone d 

0.5 

ND 

ND 

2 

NR 

2 

2 

NR 

2 

0.9 

1,1,3-Trichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

0.3 

ND 

NR 

0.6 

NR 

<1 

ND 

NR 

ND 

ND 

1,1,1 -T ribromopropanone 

>5 

ND 

NR 

ND 

NR 

ND 

ND 

NR 

ND 

NR 

1,1,3-Tribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrachloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-Tetrachloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 











Chloronitromethane 

0.2 

ND 


0.3 


0.8 




1 

Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

ND 

ND 

0.1 

ND 

0.1 

0.1 

ND 

0.1 

0.1 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.1 

ND 

ND 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin d 

0.1 

ND 

ND 

0.5 

1 

0.8 

1 

2 

2 

NR 

Bromodichloronitromethane 

0.5 

ND 


ND 


ND 




ND 

Dibromochloronitromethane 

2 

ND 


ND 


ND 




ND 

Bromopicrin 

0.5 

ND 


ND 


ND 




ND 

Miscellaneous Compounds 











Methyl ethyl ketone 

0.5 

0.7 


ND 


ND 

0.6 


ND 


Methyl tertiary butyl ether 

0.2 

ND 


ND 


ND 

ND 


ND 


1,1,2,2-Tetrabromo-2-chloroethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Benzyl chloride 

0.25 

ND 

NR 

ND 

NR 

ND 

ND 

NR 

ND 

ND 


197 














































Table 26. Additional target DBP results (ng/L) at plants 5 and 6 (4/15/02) 


4/15/2002 

Plant 5 

Plant 6 

Compound 

Raw 

OE1 

Comb FE 

PE 

D S/max 

SDS/max 

Raw 

Settled 

FE 

PE 

DS/max 

SDS/max 

Monochloroacetaldehyde 

0 

0 

0 

0.4 

0.5 

0.6 

0 

0.7 

1.6 

1.4 

2.1 

1.7 

Dichloroacetaldehyde 

0 

0 

0 

2.0 

2.0 

2.8 

0 

1.0 

2.3 

2.8 

4.9 

3.9 

Bromochloroacetaldehyde 

0 

0 

0 

0.4 

0.4 

0.6 

0 

0 

0.5 

0.5 

0.4 

0.7 

3,3-Dichloropropenoic acid 

0 

0 

0 

0.7 

0.2 

0.4 

0 

0 

0 

0 

0 

0 

Bromochloromethylacetate 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

Monochloroacetamide 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0.2 

0.8 

0.3 

Monobromoacetamide 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0.1 

2,2-Dichloroacetamide 

0 

0 

0 

0.5 

0.2 

0.5 

0 

0 

0.8 

2.7 

7.6 

9.4 

Dibromoacetamide 

0 

0 

0 

0 

0.1 

0 

0 

0 

0.1 

0.2 

0 

0.2 

Trichloroacetamide 

0 

0 

0 

0.3 

0.1 

0 

0 

0 

0.2 

1.1 

2.2 

4.1 

TOX (pg/L as CD 

26.0 


54.4 

177 

259 

247 

29.7 

90.2 

154 

210 

243 


TOBr (pg/L as Br') 

5.5 


10.1 

41.5 

36.0 

51.0 

11.9 

33.2 

25.9 


19.2 


TOC1 (pg/L as Cl') 

26.9 


25.8 

161 

194 

220 

17.3 

76.3 

152 


229 


Cyanoformaldehyde 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

5-Keto-l-hexanal 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

0.4 

6-Hydroxy-2-hexanone 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

Dimethyglyoxal 

<0.1 

0.8 

<0.1 

0.4 

0.2 

0.3 

<0.1 

<0.1 

0.5 

<0.1 

<0.1 

<0.1 

tram -2-Hexenal 

<0.1 

0.8 

0.4 

<0.1 

<0.1 

<0.1 

<0.1 

0.2 

0.1 

<0.1 <0.1 0.5 


Table 27. Halogenated furanone results (ng/L) at plants 5 and 6 (4/15/02) 


4/15/2002 

Plant 5 

Plant 6 

Compound 

Comb FE 

PE 

DS/max 

SDS/max 

Raw 

Settled 

FE 

PE 

DS/max 

BMX-1 

<0.02 

<0.02 

<0.02 (0.012) 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

BEMX-1 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

0.04 

<0.02 

<0.02 

BMX-2 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

BEMX-2 

<0.02 

0.03 

<0.02 

<0.02 

<0.02 

<0.02 

0.05 

<0.02 

0.11 

BMX-3 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

BEMX-3 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

MX 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

0.05 

<0.02 

0.09 

Red-MX 

<0.02 

<0.02 (0.01) 

<0.02 

<0.02 

<0.02 

0.02 

0.04 

0.58 

0.28 

EMX 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

ZMX 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

0.23 

<0.02 

Ox-MX 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

Mucochloric acid (ring) 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

Mucochloric acid (open) 

0.02 

0.31 

0.40 

<0.02 

<0.02 

0.02 

0.08 

0.08 

0.11 


198 






























































organic 


DBP Analyses (Laboratory) 

11/27/00 

2/26/01 

8/13/01 

10/22/01 

4/15/02 

Halogenated organic DBPs (MWDSC) 

Tables 12- 
13 

Tables 15- 
16 

Tables 18- 
19 

Tables 22- 
23 

Tables 24- 
25 

Additional target DBPs (UNC) 

Table 14 


Table 20 


Table 26 

Halogenated furanones (UNC) 



Table 21 


Table 27 

Broadscreen analysis (USEPA) 


Table 17 a 


Table 17 b 



a Plant 6 
b Plant 5 


Halomethanes. For the five sample dates, pre-ozonation/post-chlorination at plant 5 
resulted in the formation of 18-43 pg/L of the four regulated trihalomethanes (THM4) in the 
plant effluent samples. Chlorine dioxide/chlorine/chloramine disinfection at plant 6 resulted in 
the formation of 4-47 pg/L of THM4. 

Figure 6 shows the effect of bromide on THM speciation in the distribution systems of 
both utilities. Because of the lower level of bromide in this source water in February 2001 (0.04- 
0.05 mg/L), the major THM species were chloroform and bromodichloromethane, whereas in 
November 2000 (bromide = 0.08 mg/L), there was a higher mixture of brominated species 
formed. 


Figure 6 


Effect of Bromide on THM Speciation in Plant 5 Distribution System/ 
Average Detention Time: 11/27/00 Br' = 0.08 mg/L; 2/26/01 Br‘ = 0.05 mg/L 



11 / 27/2000 
2 / 26/2001 


Effect of Bromide on THM Formation and Speciation in 
Plant 6 Distribution System/Average Detention Time: 
11/27/00 Br' = 0.08 mg/L; 2/26/01 Br = 0.04 mg/L 



Figure 7 shows the impact of pre-ozonation/post-chlorination at plant 5 versus chlorine 
dioxide/chlorine/chloramine disinfection at plant 6 on THM formation and speciation for the 
August 13, 2001 sampling. On this date, both plant effluents had 26 pg/L THM4. At plant 6, 
the major THM formed was chloroform, whereas at plant 5 the major THM formed was 
bromodichloromethane. Although both plants treated water with a similar amount of bromide 
(0.05-0.06 mg/L), the amount of TOC at the point of chlorination was lower at plant 5 than at 


199 
































Figure 7 


Impact of Ozonation/Chlorination at Plant 5 versus Chlorine 
Dioxide/Chlorine/Chloramine Disinfection at Plant 6 on 
Trihalomethane Formation and Speciation (August 13, 2001) 




Plant 5 SDS/Max 
Plant 5 Eff 
Plant 6 SDS/Max 
Plant 6 Eff 


plant 6: 2.3-2.8 mg/L in the plant 5 filter effluent versus 4.5-4.7 mg/L in the plant 6 filter 
influent and effluent. At plant 5, the ozonation and biofiltration processes provided additional 
TOC reduction. As a result, the bromide-to-TOC ratio was higher at plant 5 than at plant 6. 

Other research has shown that a higher bromide-to-TOC ratio can result in a shift in speciation to 
the more brominated THMs (Symons et al., 1993). In addition, in some waters, pre-ozonation 
has been found to shift the THM formation to more brominated species (Jacanglo et al., 1989) 
because ozone converts some of the bromide to hypobromous acid. 

Because plant 6 used chloramines in the distribution system, the THMs were found to not 
increase significantly in concentration in the SDS testing in August 2001 (Figure 7), where the 
SDS/maximum sample was held for seven days. Because plant 5 used free chlorine in the 
distribution system, the THMs were found to increase in concentration in the SDS testing in 
August 2001 (Figure 7), where the SDS/maximum sample was held for seven days. In this plant 
5 SDS sample, the major THM was chloroform rather than bromodichloro-methane. The THM 
speciation at plant 5 is consistent with the difference in kinetics of halogenation between 
hypobromous acid and chlorine; that is, halogenation by hypobromous acid is quicker (Krasner 
et al., 1996). Thus, bromodichloromethane formed quicker than chloroform (plant effluent 
sample), whereas more of chloroform formed while the SDS sample was held for seven days. 

Figure 8 shows more fully the effect of reaction time on THM formation in the SDS 
testing conducted on February 26, 2001. The concentration of chloroform increased over time, 


200 




























Figure 8 


Effect of Reaction Time on THM Formation in 
Plant 5 SDS Testing (2/26/01): Time 0 = Plant Effluent 


♦—Chloroform Bromodichloromethane -a- Dibromochloromethane -X-- Bromoform 



Time (h) 


the formation of bromodichloromethane plateaued out during the SDS testing, and the amounts 
of the more brominated species were at their maximum values in the plant effluent. Again, this 
phenomenon was due to the fact that the kinetics of brominated DBP formation are faster than 
the kinetics of chlorinated DBP formation (Krasner et al., 1996). 

In addition, low levels of certain iodinated THMs (e.g., dichloroiodomethane) were 
detected in selected samples, especially at plant 6 (Figure 9). In October 2001, 3 pg/L of 
dichloroiodomethane was detected in the plant 6 effluent, whereas 0.5 pg/L was detected in the 
plant 5 effluent. Bromochloroiodomethane was also detected in the plant 6 effluent in February 
2001 using broadscreen GC/MS techniques (Table 17). Waters that contain bromide may also 
contain iodide. Iodide is oxidized to hypoiodous acid in the presence of ozone, chlorine, or 
chloramines (Bichsel and von Gunten, 2000). Hypoiodous acid can react with the TOC to form 
iodinated THMs. Bichsel and von Gunten (2000) found that ozone could also oxidize iodide to 
iodate and, depending on ozonation conditions, form little to no iodinated THMs; whereas 
chlorine lead to the formation of iodate and iodinated THMs. Although iodate was not measured 
in this study, the use of ozone at plant 5 did result in the formation of less iodinated THMs in the 
finished water than at plant 6. 

Haloacids. Pre-ozonation/post-chlorination at plant 5 resulted in the formation of 10-34 
pg/L of the five regulated haloacetic acids (HAA5) in the plant effluent samples, whereas 
chlorine dioxide/chlorine/chloramine disinfection at plant 6 resulted in the formation of 20-68 


201 












Figure 9 


Seasonal Formation of Dichloroiodomethane at 
Plant 6 and Plant 5: Plant Effluent Samples 



pg/L of HAA5. In addition, all nine HAAs (HAA9) were measured, which includes all of the 
brominated HAA species. The levels of HAA9 in the plant 5 effluent were 20-56 pg/L, whereas 
the levels of HAA9 in the plant 6 effluent were 25-88 pg/L. 

Figure 10 shows the effect of bromide on HAA speciation in SDS testing at plant 5 (a 
similar effect was observed at plant 6). Because of the lower level of bromide in this water in 
February 2001, the two major HAAs were di- and trichloroacetic acid (DCAA and TCAA), 
whereas in November 2000 there was a higher mixture of brominated species formed. 

Figure 11 shows the effect of the two disinfection schemes on the seasonal formation of 
THMs and HAAs in the plant effluents of plant 5 and plant 6. At plant 5, the sum of the 
dihalogenated HAAs (DXAAs) was somewhat higher than the sum of the trihalogenated HAAs 
(TXAAs) (Figure 11). This is consistent with the research of Reckhow and Singer (1984), in 
which ozonation was found to control the formation of TCAA better than that of DCAA. 

At plant 6, in the settled water after chlorine dioxide disinfection, almost all of the HAAs 
that were formed were DXAAs; no TXAAs were detected (Figure 12). (In addition, the level of 
THMs was almost non-detectable at this sample location.) At this point in the treatment process, 
only chlorine dioxide disinfection had been utilized. In other DBP research, chlorine dioxide has 
been shown to produce little or no THMs and TXAAs, whereas DXAAs were formed (Zhang et 
al., 2000). After the addition of free chlorine at plant 6, the levels of HAAs increased, including 
the formation of TXAAs (Figure 12). However, DXAAs still predominated in the plant 6 
samples (more so than at plant 5) (Figure 11). 


202 









Figure 10 


Effect of Bromide on HAA Speciation in Plant 5 SDS Testing/ 
Average Detention Time: 11/27/00 Br' = 0.08 mg/L; 2/26/01 Br' = 0.05 mg/L 





<n° 

vcy cP 


/'//// / j * > 






<> N 


^ 


11 / 27/2000 

2 / 26/2001 


f / / / / / 

* ^ 

,o^ <o s ^ 

* 


<& 


Figure 11 


Seasonal Formation of Trihalomethanes and Haloacetic Acids 
at Plant 5 and Plant 6: Plant Effluent Samples 



CL 

GQ 

O 



Plant 5 
THM4 


Plant 5 
TXAAs 


Plant 5 
DXAAs 


Plant 6 
THM4 


Plant 6 
TXAAs 


Plant 6 
DXAAs 


13-Aug-01 
26-Feb-01 
27-Nov-OO 


203 



























Figure 12 


Effect of Chlorine Dioxide/Chlorine/Chloramine Disinfection at Plant 6 
on HAA Formation and Speciation: 2/26/01 


■ DXAA DTXAA 



In the presence of chlorine, HAAs were formed in the plant 5 SDS testing (Figure 13). 
The SDS/average samples for plant 5 in November 2000 - August 2001 were held for three days. 
The increase in formation of the DXAAs was much higher than for the TXAAs, which may be 
due (in part) to the ability of ozone to better destroy TXAA precursors. In the presence of 
chloramines, HAA concentrations were typically stable within analytical variability in the plant 6 
SDS testing (Figure 13). The SDS/average samples for plant 6 in November 2000 - August 2001 
were held for four days. 

In addition to the target HAAs, other haloacids were detected in selected samples by the 
broadscreen GC/MS methods (Table 17). Plant 6—which had 0.04 mg/L bromide in February 
2001—produced two other chlorinated acids (i.e., di- and trichloropropenoic acid). These were 
detected following the chlorine dioxide disinfection. A different chlorinated acid was detected at 
plant 5 after post-chlorination (3,4,4-trichloro-3-butenoic acid). 

UNC detected 3,3-dichloropropenoic acid in finished waters from several samplings 
(plant 5 and plant 6, November 2000; plant 6, August 2001; and plant 5, April 2002). Levels 
ranged from 0.7 to 4.7 pg/L in the finished waters, and generally increased in concentration in 
the distribution system. 

Haloacetonitriles. In other research, haloacetonitriles (HANs) have been found to be 
produced at approximately one-tenth the level of the THMs (Oliver, 1983). This was also 
generally observed in the plant 5 and plant 6 samples (Figure 14). Trichloroacetonitrile 
(TCAN)—an Information Collection Rule (ICR) DBP—was not detected. Likewise, the 


204 






























































Figure 13 


Impact of Residual Disinfectant on Formation of Haloacetic Acids in 
Simulated Distribution System Samples with Average Detention Time: 
Chlorine at Plant 5, Chloramines at Plant 6 



Figure 14 


Relationship of the Sum of HANs (up to 6 Species) to THM4 

at Plant 5 and Plant 6 


Filter Eff ■ Clear. Eff □ Plant Eff 0 DS/Ave 0 DS/Max □ SDS/Ave ■ SDS/Max 


20% n 


(A 

<A 

ro 

-Q 

+■* 

JC 

O) 

'53 

S 

I 

E 

3 

(A 

z 

< 

I 


15 % 



10 % 


Plant 6 (11/27/00) Plant 6 (2/26/01) Plant 5 (11/27/00) Plant 5 (2/26/01) 


205 












































































brominated analogues of TCAN were not detected in the plant 5 samples. However, at plant 6, 
dibromochloroacetonitrile was detected in an SDS sample in October 2001 and 
tribromoacetonitrile was detected in February 2001 by the broadscreen GC/MS methods (Table 
17). In addition, sub-pg/L levels of another target HAN (i.e., chloroacetonitrile) were detected in 
selected samples at both utilities. 

Haloketones. The level of 1,1,1 -trichloropropanone (1,1,1 -TCP)—which is a precursor 
to chloroform formation—was higher at plant 5 (Figure 15). More of this haloketone (HK) 
formed with free chlorine than with chloramines. The level of 1,1-dichloropropanone (1,1-DCP) 
was typically higher at plant 6 (Figure 15). The latter compound was often detected in the settled 
water after chlorine dioxide disinfection. Thus, at plant 6, chlorine dioxide and chloramines 
were found to be better at controlling the formation of 1,1,1-TCP (and THMs and TXAAs) than 
the formation of 1,1-DCP (and DXAAs). 


Figure 15 

Effect of Ozone/Chlorine Disinfection at Plant 5 and 
Chlorine Dioxide/Chlorine/Chloramine Disinfection at Plant 6 
on the Formation of Haloketones 

□ Settled ■ Filter Eff □ Clear. Eff m Plant Eff □ DS/Ave □ DS/Max ■ SDS/Ave PSDS/Max 



Plant 6 (11/27/00) Plant 6 (2/26/01) Plant 5 (11/27/00) Plant 5 (2/26/01) 

In addition to the formation of low levels of HK compounds from the ICR (i.e., 1,1-DCP 
and 1,1,1-TCP), low levels of some of the target HKs were detected in selected samples. In 
addition to the target HKs, other HKs were detected in selected samples by the broadscreen 
GC/MS methods (Table 17). A number of these HKs were analogous to the di- and 
tetrahalogenated target HKs, except that these were mixed bromochloro species. 

Haloaldehydes. In addition to the formation of chloral hydrate (trichloroacetaldehyde)— 
an ICR DBP—dichloroacetaldehyde was formed. The level of chloral hydrate was higher at 
plant 5. More of this DBP formed with free chlorine than with chloramines. On the other hand, 


206 














































dichloroacetaldehyde was often higher in concentration at plant 6. In addition, brominated 
analogues of both of these haloacetaldehydes were detected in selected samples. 

In addition to the target haloaldehydes, two other haloaldehydes were detected in selected 
samples by the broadscreen GC/MS methods (Table 17). Another brominated aldehyde 
(2-bromo-2-methylpropanal) and an iodinated aldehyde were detected (tentatively identified as 
iodobutanal). This is the first report of an iodoaldehyde as a DBP in drinking water. High 
resolution mass spectrometry confirmed the presence of the iodine in the structure of this 
molecule, and also its overall empirical formula (C4H7OI, molecular weight of 198). At this 
point, the identification is tentative, however—it is highly likely that the molecule is an iodo¬ 
aldehyde with four carbons, but the exact isomer assignment cannot be determined by its mass 
spectrum. An attempt to obtain synthetic standards of iodobutanal forms is currently underway 
in order to obtain a confirmed assignment. 

Halonitromethanes. Low levels of chloropicrin (trichloronitromethane) (an ICR DBP) 
were detected. Other halonitromethanes (HNMs) were detected in selected samples. The levels 
of chloropicrin and the bromine-containing trihalonitromethanes were higher at plant 5 
(Figure 16). Other research has shown that pre-ozonation can increase the formation of 
chloropicrin upon post-chlorination (Hoigne and Bader, 1988). Similar to the THM speciation in 
the plant effluent samples in August 2001 (Figure 7), in terms of the trihalonitromethanes, mixed 
bromochloro species predominated at plant 5, whereas the trichloro species was the only 
trihalonitromethane detected at plant 6 on that sample date (Figure 16). 

Figure 16 

Impact of Ozonation/Chlorination at Plant 5 versus 
Chlorine Dioxide/Chlorine/Chloramine Disinfection at 
Plant 6: Plant Effluents (August 13, 2001) 


Plant 5 
6 



207 










The relative speciation of brominated and chlorinated HNMs (for the di- and 
trihalogenated species) was compared to the HAAs, THMs, and the dihaloacetonitriles (DHANs) 
for the August 2001 data. Each DBP can be abbreviated based on the number of halogens and 
the speciation of the halogens as follows: RBr y Cl z , where the number of bromine and chlorine 
atoms are y and z, respectively, and R corresponds to the remainder of the DBP molecule (i.e., 
carbon, hydrogen, oxygen, and nitrogen atoms). The concentration of each DBP was 
“normalized” by dividing its concentration by the sum of the concentrations of all of the DBPs 
for that “subclass” of DBPs (RX y+z ) (Figure 17). For example, the concentration of DCAA was 
divided by the sum of all the DXAAs. 

Figure 17. Plant 5 effluent (August 13, 2001) 


Relative Speciation of Brominated and Chlorinated DBPs: 
Halonitromethanes (HNMs), Haloacetic Acids (HAAs), 
Dihaloacetonitriles (DHANs), Trihalomethanes (THMs) 



For the dihalogenated DBPs (RX 2 ), the dichlorinated species represented 53 to 78 % of 
the sum of the dihalogenated DBPs in that class of DBPs. The bromochloro species represented 
22 to 33 % of the class sum, and the dibromo species represented 0 to 21 % of the class sum. For 
the trihalogenated DBPs (RX 3 ), the trichlorinated, bromodichlorinated, dibromochlorinated, and 
tribrominated species represented 20 to 53 %, 35 to 43 %, 12 to 40 %, and 0 to 2 % of the class 
sum, respectively. For the THMs, HAAs, DHANs, and HNMs, there was a similar relative 
speciation of brominated and chlorinated DBPs for the dihalogenated species and a similar 
relative speciation of brominated and chlorinated DBPs for the trihalogenated species. 

Halogenatedfuranones. Tables 21 and 27 show the results for halogenated furanones in 
the August 2001 and April 2002 samplings for plant 5 and plant 6 . Data are included for 3- 
chloro-4-(dichloromethyl)-5-hydroxy-2[5H]-furanone, otherwise known as MX; (E)-2-chloro-3- 
(dichloromethyl)-4-oxobutenoic acid, otherwise known as EMX; (Z)-2-chloro-3- 


208 




























(dichloromethyl)-4-oxobutenoic acid (ZMX); the oxidized form of MX (Ox-MX); the reduced 
form of MX (Red-MX); brominated forms of MX and EMX (BMXs and BEMXs); and 
mucochloric acid (MCA), which can be found as a closed ring or in an open form. Results are 
displayed graphically in Figures 18 and 19. 

The combination of ozonation and biofiltration (with GAC filters) removed MX and MX- 
analogue precursors in plant 5, whereas chlorine dioxide pretreatment at plant 6 did not. At plant 
6 , intermediate chlorination and chloramine post-disinfection produced MX and MX-analogues 
(Tables 21 and 27). In August 2001, MX was not detected at the plant 6 filter effluent, whereas 
it was detected in the plant 6 effluent (310 ng/L) (Figure 18). Alternatively, EMX was detected 
at the plant 6 filter effluent (230 ng/L), but it was not detected in the plant effluent. EMX is the 
open ring analogue of MX, and these two halogenated furanones are in equilibrium with each 
other. It appears as if EMX may have been converted to MX between the plant 6 filter effluent 
and the plant effluent. 

In the second sampling of plants 5 and 6 (4/15/02) for halogenated furanones, brominated 
MX-analogues were also measured, but did not appear, except in low concentrations (up to 50 
ng/L) (Figure 19), within plant 6 due to the low concentration of bromide (0.06 mg/L) in the 
source water. The reduced form of MX (red-MX) increased in concentration from the filter 
effluent (40 ng/L) to the plant effluent (580 ng/L) at plant 6 due to residual chloramines (3.2 
mg/L) reaction with TOC (3.88 mg/L). Mucochloric acid (MCA open) was detected in the plant 
effluent (310 ng/L) of plant 5 due to the filter effluent chlorine (2.5 mg/L dose) and clearwell 
effluent chlorine (1.02 mg/L dose) reacting with the TOC (~3.5 mg/L) of the combined filter 
effluent. 


0.45 
0.40 
o 0.35 
% S 0.30 

k. w 

3 C 

u- O 0.25 

TJ *i 
0 ) (0 

ra ~ 0.20 

Is 

c 0.15 

.2 o 
ra O 

I 0.10 
0.05 


0.00 


Figure 18 

Plants 5 and 6(8/13/01) 


I MX 13ZMX 11 EMX DMCA (ring) 01 MCA (open) 


GAC FE 
03+GAC 


PE 


Plant 5 


■ I 




DS/ave 


CI2 


Raw 


Settled 

CI02 


FE 

CI2+Filter 
Plant 6 


■ I 


PE DS/ave 

CI2+NH3 


Sampling Point 


209 






































Figure 19 


Plants 5 and 6 (4/15/02) 


□ BMX-1 

□ BEMX-1 

■ BMX-2 

■ BEMX-2 

■ BMX-3 

□ BEMX-3 ■ MX 

■ Red-MX 

HEMX 

■ ZMX 

□ Ox-MX 

□ MCA (ring) 

■ MCA (open) 


1.00 


0.90 


o ^ 0.80 

c _J 

c w 0.70 

ro >3 


0.60 


■o 


(0 

c 
o 

~ 0.50 


ra 

c 

0 ) 


c 

<D 


CD O 

o c 
ro o 
I O 


0.40 


0.30 


0.20 


0.10 

0.00 



Comb FE 


PE 


DS/max 


SDS/max 


Raw 


Settled 


FE 


PE DS/max 


03+GAC | 


CI2 


CI02 


CI2+Filter 


CI2+NH3 


Plant 5 


Plant 6 


Sampling Points 


210 






























































Volatile Organic Compounds. Methyl ethyl ketone (MEK) was detected in the raw water 
of both plants on August 13, 2001 at concentrations of 3-7 pg/L. The level of MEK decreased 
through the treatment plant and in the distribution system. MEK was detected in the raw water 
on October 22, 2001 and April 15, 2002 at 0.6-0.7 pg/L and in other selected samples at similar 
concentrations. Methyl tertiary butyl ether (MtBE) was detected in the raw water of both plants 
on August 13, 2001 at a concentration of 0.3-0.4 pg/L. The level of MtBE was unchanged 
through the treatment plant. MEK is an industrial solvent and MtBE is a gasoline additive. 

Other Halogenated DBPs. A few additional, miscellaneous halogenated DBPs were also 
detected. UNC methods detected dichloroacetamide at 1.5, 5.6, and 2.7 pg/L in finished water 
from plant 6 (11/27/00, 8/13/01, and 4/15/02) (Tables 14, 20, and 26). Dichloroacetamide was 
also observed in finished water from plant 5 at 0.5 pg/L in April 2002 (Table 26). Levels either 
increased or remained fairly steady in the distribution system and in SDS testing. Also, four 
additional haloamides— monochloroacetamide, monobromoacetamide, dibromoacetamide, and 
trichloroacetamide—were found in finished water samples collected in April 2002 from both 
plants (Table 26). Bromochloromethylacetate was observed in November 2000 in finished 
waters from plant 6(1.1 pg/L), but was not detected in the distribution system or SDS testing 
(Table 14), presumably due to degradation. 

Broadscreen GC/MS analyses revealed the presence of hexachlorocyclopentadiene and 
dichloroacetic acid methyl ester in finished water collected from plant 6 in February 2001 (Table 
17). These compounds were not observed in the corresponding raw, untreated water. 

Non-Halogenated DBPs. A few non-halogenated DBPs were detected in finished waters 
from plant 5 and plant 6. Dimethylglyoxal was identified at 2.1 and 1.7 pg/L in finished waters 
from plant 5 and plant 6, respectively (November 2000, Table 14). It was also found in later 
samplings from both plants (Tables 20 and 26), and it did not appear to degrade in the 
distribution system. 7nms-2-hexenal was also identified in waters from two samplings (Tables 
14 and 26) and appears to be formed both by ozonation and treatment with chlorine dioxide. 
However, it does not appear to be stable; levels were diminished at the plant effluent. 

Broadscreen GC/MS analysis revealed the presence of glyoxal and methyl glyoxal in 
both the ozone effluent and the finished water from plant 5 (Table 17). Also, decanoic acid and 
hexadecanoic acid were found in finished waters from plant 6 at levels significantly higher than 
in the raw, untreated water (Table 17). 


REFERENCES 

Aieta, E. M., and J. D. Berg. A review of chlorine dioxide in drinking water treatment. Journal 
of the American Water Works Association 78(6):62 (1986). 

American Public Health Association (APHA). Standard Methods for the Examination of Water 
and Wastewater, 20th ed. APHA, American Water Works Association, and Water Environment 
Federation: Washington, DC (1998). 


211 


Bichsel, Y., and U. von Gunten. Formation of iodo-trihalomethanes during disinfection and 
oxidation of iodide-containing waters. Environmental Science & Technology 34(13):2784 
( 2000 ). 

Bolyard, M., P. S. Fair, and D. P. Hautman. Occurrence of chlorate in hypochlorite solutions 
used for drinking water disinfection. Environmental Science & Technology 26(8): 1663 (1992). 

Delcomyn, C. A., H. S. Weinberg, and P. C. Singer. Measurement of sub-pg/L levels of bromate 
in chlorinated drinking waters. Proceedings of the American Water Works Association Water 
Quality Technology Conference, American Water Works Association: Denver, CO, 2000. 


Douville, C. J., and G. L. Amy. Influence of natural organic matter on bromate formation during 
ozonation of low-bromide drinking waters: a multi-level assessment of bromate. In Natural 
Organic Matter and Disinfection By-Products: Characterization and Control in Drinking Water 
(S.E. Barrett, S.W. Krasner, & G.L. Amy, eds.), pp. 282-298, American Chemical Society: 
Washington, D.C., 2000. 

Hoigne, J., and H. Bader. The formation of trichloronitromethane (chloropicrin) and chloroform 
in a combined ozonation/chlorination treatment of drinking water. Water Research 22(3):313 
(1988). 

Krasner, S. W., W. H. Glaze, H. S. Weinberg, P. A. Daniel, and I. N. Najm. Formation and 
control of bromate during ozonation of waters containing bromide. Journal of the American 
Water Works Association 85(1):73 (1993). 

Krasner, S. W., M. J. Sclimenti, R. Chinn, Z. K. Chowdhury, and D. M. Owen. The impact of 
TOC and bromide on chlorination by-product formation. In Disinfection By-Products in Water 
Treatment: The Chemistry of Their Formation and Control (R.A. Minear and G.L. Amy, eds.), 
pp. 59-90, CRC Press/Lewis Publishers: Boca Raton, FL, 1996. 

Kuo, C.-Y., H.-C. Wang, S. W. Krasner, and M. K. Davis. Ion-chromatographic determination 
of three short-chain carboxylic acids in ozonated drinking water. In Water Disinfection and 
Natural Organic Matter: Characterization and Control (R.A. Minear & G.L. Amy, eds.), pp. 
350-365, American Chemical Society: Washington, D.C., 1996. 

Oliver, B. G. Dihaloacetonitriles in drinking water: algae and fulvic acid as precursors. 
Environmental Science & Technology 17(2):80 (1983). 

Reckhow, D. A., and P. C. Singer. The removal of organic halide precursors by preozonation 
and alum coagulation. Journal of the American Water Works Association 76(4): 151 (1984). 

Symons, J. M., S. W. Krasner, L. A. Simms, and M. J. Sclimenti. Measurement of THM and 
precursor concentrations revisited: the effect of bromide ion. Journal of the American Water 
Works Association 85( 1 ):51 (1993). 


212 


van der Kooij, D., A. Visser, and W. A. M. Hijnen. Determining the concentration of easily 
assimilable organic carbon in drinking water. Journal of the American Water Works Association 
74(10):540 (1982). 

van der Kooij, D., and W. A. M. Hijnen. Substrate utilization by an oxalate consuming Spirillum 
species in relation to its growth in ozonated water. Applied Environmental Microbiology 47:551 
(1984). 

Volk, C. J., and M. W. LeChevallier. Effects of conventional treatment on AOC and BDOC 
levels. Journal of the American Water Works Association 94(6): 112 (2002). 

Zhang, X., S. Echigo, R. A. Minear, and M. J. Plewa. Characterization and comparison of 
disinfection by-products of four major disinfectants. In Natural Organic Matter and 
Disinfection By-Products: Characterization and Control in Drinking Water (S. E. Barrett, S. W. 
Krasner, and G. L. Amy, eds.), pp. 299-314, American Chemical Society: Washington, D.C., 
2000 . 


213 


EPA REGION 3: PLANTS 3 AND 4 


Plant Operations and Sampling 

On November 13, 2000, February 5, 2001, August 1, 2001, October 16, 2001, and 
January 28, 2002, plants 3 and 4 (EPA Region 3) were sampled. Plants 3 and 4 operated in 
parallel on a common source water (Figures 1-2). 

The treatment processes at plant 3 (Figure 3) included flocculation, coagulation, 
sedimentation, and filtration. The settled water was first filtered through a multimedia filter and 
then through a granular activated carbon (GAC) filter. The raw water was disinfected with free 
chlorine. In November 2000, August 2001, and October 2001, ammonia was added to convert 
the chlorine to chloramines after a 30-sec or 1-min chlorine contact time, whereas ammonia was 
not added until the plant effluent in February 2001. (Information on the disinfection scheme for 
January 2002 is not available.) After the GAC and at the plant effluent, additional chlorine was 
added. In addition, in August and October 2001, chlorine was applied at the end of the 
sedimentation basin. 

The treatment processes at plant 4 (Figures 1-2) included flocculation, coagulation, 
sedimentation, and filtration. The settled water was filtered through a GAC filter. Chlorine was 
applied to the raw and filtered waters and at the plant effluent. Chloramines were not used at 
plant 4. 

Plant 3 was sampled at the following locations (Figure 3): 

(1) raw water 

(2) the rapid mix effluent (prior to ammonia addition) 

(3) the GAC influent 

(4) the GAC effluent 

(5) the plant effluent 

Plant 4 was sampled at the following locations: 

(1) GAC influent 

(2) GAC effluent 

(3) the plant effluent 

In addition, plant effluent samples were collected for both plants, and simulated distribution 
system (SDS) testing was conducted for average and maximum detention times for that time of 
year (Table 1). Furthermore, the distribution systems for both plants were sampled at two 
locations, one representing an average detention time and the other representing a maximum 
detention time. (Raw water was not sampled at plant 4, as it is the same as is used at plant 3.) 


214 


3 Stage 
Flocculation 




215 
































































































Figure 3. Simplified line diagram of chemical application and sampling points at plant 3. 


Table 1. SDS holding times (hr) at plants 3 and 4 


Sample 

11/13/00 

2/5/01 

8 /1/01 

10/16/01 

1/28/02 

Plant 3 average detention time 

20 

18 

18 

77 

NA a 

Plant 3 maximum detention time 

28 

48 

48 

140 

NA 

Plant 4 average detention time 

20 

20 

8 

77 

NA 

Plant 4 maximum detention time 

28 

30 

24 

140 

NA 


a NA = Not available 


On the day of sampling, information was collected on the operations at each plant 
(Tables 2-3). In February 2001, several of the plant 4 filters had been removed from service. In 
order to maintain filtered water quality on the plant 4 side, plant 3 carbon contactor filtered 
(CCF) water was added to the plant 4 suction (clearwell). Thus, 6.0 million gallons per day 
(mgd) of plant 3 CCF water was added to the plant 4 side. This resulted in 35 % of the plant 4 
water being plant 3 CCF water. This affected the results of the plant 4 distribution-system and 
SDS samples. Likewise, in August and October 2001, blending occurred at the entrance to the 
plant 4 distribution system, which was a combination of plant 4 and “deep bed GAC” filtered 
waters (the plant 4 effluent was a combination of water from the plant 3 clearwell and the plant 4 
clearwell). 


216 

























































































Table 2. Operational information at plant 3 


Parameter 

11/13/00 

2/5/01 

8 /1/01 

10/16/01 

1/28/02 

Plant flow (mgd) 

8 

10 

9 

9 

NA 

Coagulant 3 dose (mg/L) 

60 

39 

56 

91 

NA 

GAC filter loading rate (gpm/sq ft) 

6.14 

7.7 

6.91 

6.91 

NA 

GAC EBCT b (min) 

14.9 

11.9 

13.3 

13.3 

NA 

Chlorine dose at rapid mix (mg/L) 

3.3 

5.7 

6.6 

6.6 

NA 

Ammonia dose at rapid mix eff. (mg/L as N) 

0.55 

0 

0.9 

0.9 

NA 

Chlorine dose at end of sed. basin (mg/L) 

0 

0 

4.0 

3.0 

NA 

Chlorine dose at GAC effluent (mg/L) 

1.2 

1.2 

1.3 

1.3 

NA 

Chlorine dose at plant effluent (mg/L) 

2.05 

2.5 

2.03 

2.8 

NA 

Ammonia dose at plant effluent (mg/L as N) 

0.85 

0.90 

0.82 

0.94 

NA 


a Aluminum sulfate [A^SO^ MH 2 O] 
b Empty bed contact time 


Table 3. Operational information at plant 4 


Parameter 

11/13/00 

2/5/01 

8 /1/01 

10/16/01 

1/28/02 

Plant flow (before addition of plant 3 GAC 
effluent) (mgd) 

11.8 

11 

11 

9.9 

NA 

Flow of plant 3 GAC effluent added to plant 

4 (mgd) 

0 

6.0 

4.2 

4.9 

NA 

Coagulant 3 dose (mg/L) 

60 

39 

56 

91 

NA 

GAC filter loading rate (gpm/sq ft) 

1.3 

1.2 

1.13 

1.01 

NA 

GAC EBCT (min) 

11.5 

12.9 

13.3 

14.8 

NA 

Chlorine dose at rapid mix (mg/L) 

4.5 

5.7 

7.6 

6.0 

NA 

Chlorine dose at entrance of plant 4 (filtered 
water) clearwell (mg/L) 

NA 

NA 

1.35 

1.21 

NA 

Chlorine dose at plant effluent (mg/L) 

0.6 

0.4 

1.2 

0.9 

NA 


a Aluminum sulfate 


Water Quality 

On the day of sampling, information was collected on the water quality at each plant 
(Tables 4-5). At plant 3, seasonal control of disinfection by-products (DBPs)—especially 
trihalomethanes (THMs)—was being achieved using pre-chloramination. During warmer 
months (e.g., August, October, November), ammonia was added to convert the chlorine to 
chloramines after a 1-min chlorine contact time, whereas ammonia was not added until the plant 
effluent during colder months (e.g., February). 


217 

































Table 4. Water quality information at plant 3 



pH 

Temperature (°C) 

Disinfectant Residual 3 (mg/L) 

Location 

11/13/00 

2/5/01 

8/1/01 

10/16/01 

1/28/02 

11/13/00 

2/5/01 

8/1/01 

10/16/01 

1/28/02 

11/13/00 

2/5/01 

8/1/01 

10/16/01 

1/28/02 

Raw 

7.3 

6.9 

7.3 

7.6 

NA 

13.9 

7 

25.6 

18.9 

NA 

— 

— 

— 

— 

NA 

RM b eff. 

6.1 

5.9 

6.3 

6.0 

NA 

13.9 

7 

25.6 

18.9 

NA 

2.2 

3.5 

3.2 

3.2 

NA 

GAC inf. 

6.2 

5.5 

6.0 

6.0 

NA 

13.9 

9 

25.6 

18.1 

NA 

0.9 

0.5 

1.6 

1.6 

NA 

GAC eff. 

6.0 

5.5 

6.1 

5.9 

NA 

13.9 

8 

24.6 

18.9 

NA 

0.1 

0 

ND C 

ND 

NA 

Plant eff. 

7.4 

7.2 

7.4 

7.4 

NA 

13.9 

10 

25.6 

19.6 

NA 

3.2 

3.5 

3.1 

3.8 

NA 

DS d /ave. 

7.5 

7.2 

7.4 

7.4 

NA 

13.9 

9 

26.4 

20.2 

NA 

2.5 

2.6 

2.8 

2.8 

NA 

D S/max 

7.3 

7.2 

7.4 

7.4 

NA 

13.9 

9 

26.4 

20.2 

NA 

2.0 

2.4 

2.4 

2.4 

NA 

SDS/ave. 

7.4 

7.2 

7.4 

7.4 

NA 

13.9 

9 

24.5 

20.2 

NA 

2.5 

2.3 

2.8 

2.4 

NA 

SD S/max 

7.5 

7.2 

7.4 

7.4 

NA 

13.9 

9 

24.5 

20.2 

NA 

2.4 

2.0 

2.4 

2.0 

NA 


a l 1/13/00, 8/1/01, 10/16/01: Chlorine residuals (values shown in italics) at rapid mix effluent; chloramine (or total) residuals at other locations 
2/5/01: Chlorine residuals (values shown in italics) at rapid mix effluent, GAC influent and effluent; chloramine residuals at other locations 
b RM = Rapid mix 
C ND = Not detected 
d DS = Distribution system 


Table 5. Water quality information at plant 4 



PH 

Temperature (°C) 

Chlorine Residual (mg/L) 

Location 

11/13/00 

2/5/01 

8/1/01 

10/16/01 

1/28/02 

11/13/00 

2/5/01 

8/1/01 

10/16/01 

1/28/02 

11/13/00 

2/5/01 

8/1/01 

10/16/01 

1/28/02 

GAC inf. 

6.2 

5.5 

6.1 

6.0 

NA 

13.9 

7 

25.6 

18.9 

NA 

2.6 

1.4 

1.5 

0.9 

NA 

GAC eff. 

6.2 

5.5 

6.0 

6.0 

NA 

13.9 

7 

24.5 

18.9 

NA 

0.6 

0.8 

0.4 

0.4 

NA 

Plant eff. 

7.2 

6.8 

6.9 

7.2 

NA 

13.9 

8 

24.5 

19.6 

NA 

1.1 

1.2 

1.2 

1.2 

NA 

DS/ave. 

7.0 

6.5 

6.9 

7.2 

NA 

13.9 

8 

25.2 

20.2 

NA 

1.8 

1.0 

0.8 

1.0 

NA 

DS/max 

6.8 

6.5 

6.9 

7.0 

NA 

13.9 

9 

25.2 

20.2 

NA 

1.2 

0.5 

0.9 

0.8 

NA 

SDS/ave. 

7.1 

6.2 

6.9 

7.0 

NA 

13.9 

9 

24.5 

20.2 

NA 

1.4 

0.5 

0.8 

0.7 

NA 

S DS/max 

7.1 

6.2 

6.9 

7.0 

NA 

13.9 

9 

24.5 

20.2 

NA 

1.1 

0.5 

0.8 

0.4 

NA 


218 

























































Data were also collected for total organic carbon (TOC) and ultraviolet (UV) absorbance 
(Table 6). The TOC ranged from 4.3 to 6.4 mg/L, and the UV absorbance from 0.090 to 0.187 
cm '. At plants 3 and 4, coagulation removed 30-59 % of the TOC and GAC filtration removed 
another 4-23 %. At plant 3, GAC filtration was used to prevent taste-and-odor problems in the 
finished water and for the removal of other micropollutants, but it was not installed for DBP 
precursor (TOC) removal. The GAC is only regenerated once every three years at plant 3. At 
plants 3 and 4, coagulation, GAC filtration, and chlorination cumulatively reduced the UV 
absorbance by 67-84 %. 


Table 6. TOC and UV removal at plants 3 and 4 


Location 

TOC 

(mg/L) 

UV a 

(cm' 1 ) 

SUVA 15 

(L/mg-m) 

Remova 

/Unit (%) 

Removal/Cumulative (%) 

TOC 

UV 

TOC 

UV 

11/13/2000 








Raw water 

4.37 

0.091 

2.08 

— 

— 

— 

— 

Plant 3 GAC inf. 

2.34 

0.041 

1.75 

46% 

55% 

46% 

55% 

Plant 3 GAC eff. 

2.2 

0.028 

1.27 

6.0% 

32% 

50% 

69% 

Plant 4 GAC inf. 

2.47 

0.027 

1.09 

43% 

70% 

43% 

70% 

Plant 4 GAC eff. 

2.31 

0.029 

1.26 

6.5% 

-7.4% 

47% 

68% 

02/05/2001 








Raw water 

6.44 

0.187 

2.90 

— 

— 

— 

— 

Plant 3 GAC inf. 

2.63 

0.038 

1.44 

59% 

80% 

59% 

80% 

Plant 3 GAC eff. 

2.46 

0.033 

1.34 

6.5% 

13% 

62% 

82% 

Plant 4 GAC inf. 

2.70 

0.036 

1.33 

58% 

81% 

58% 

81% 

Plant 4 GAC eff. 

2.59 

0.033 

1.27 

4.1% 

8.3% 

60% 

82% 

08/01/2001 








Raw water 

6.25 

0.14 

2.24 

— 

— 

— 

— 

Plant 3 GAC inf. 

2.63 

0.034 

1.29 

58% 

76% 

58% 

76% 

Plant 3 GAC eff. 

2.02 

0.023 

1.14 

23% 

32% 

68% 

84% 

Plant 4 GAC inf. 

3.24 

0.03 

0.93 

48% 

79% 

48% 

79% 

Plant 4 GAC eff. 

2.69 

0.032 

1.19 

17% 

-6.7% 

57% 

77% 

10/16/2001 








Raw water 

5.9 

0.113 

1.92 

— 

— 

— 

— 

Plant 3 GAC inf. 

2.87 

0.036 

1.25 

51% 

68% 

51% 

68% 

Plant 3 GAC eff. 

2.37 

0.028 

1.18 

17% 

22% 

60% 

75% 

Plant 4 GAC inf. 

4.13 

0.047 

1.14 

30% 

58% 

30% 

58% 

Plant 4 GAC eff. 

3.58 

0.037 

1.03 

13% 

21% 

39% 

67% 

01/28/2002 








Raw water 

4.27 

0.090 

2.11 

— 

— 

— 

— 

Plant 3 GAC inf. 

2.40 

0.030 

1.25 

44% 

67% 

44% 

67% 

Plant 3 GAC eff. 

2.23 

0.029 

1.30 

7.1% 

3.3% 

48% 

68% 

Plant 4 GAC inf. 

2.85 

0.031 

1.09 

33% 

66% 

33% 

66% 

Plant 4 GAC eff. 

2.45 

0.029 

1.18 

14% 

6.5% 

43% 

68% 


a UV = Ultraviolet absorbance reported in units of "inverse centimeters" (APHA, 1998) 
bSUVA (L/mg-m) = Specific ultraviolet absorbance = 100*UV (cm-1)/DOC (mg/L) or UV (m-1)/DOC (mg/L), 
where DOC = dissolved organic carbon, which typically = 90-95% TOC (used TOC values in calculating SUVA) 
(e.g., UV = 0.091/cm = 0.091/(0.01 m) = 9.1/m, DOC = 4.37 mg/L, SUVA = (9.1 m-1)/(4.37 mg/L) = 2.08 L/mg-m) 


219 









































Table 7 shows other water quality parameters for the raw source water for plants 3 and 4. 
Note, that source water received a tremendous amount of rainfall the weekend before the August 
2001 sampling, which may have diluted some of these water quality parameters. 

Table 7. Miscellaneous water quality parameters in plants 3 and 4 raw water 


Date 

Bromide 

(mg/L) 

Alkalinity 

(mg/L) 

Ammonia 
(mg/L as N) 

11/13/2000 

0.058 

69 

0.07 

02/05/2001 

0.022 

27 

0.1 

08/01/2001 

0.05 

49 

0.08 

10/16/2001 

0.2 

61 

0.09 

01/28/2002 

0.023 

38 

0.12 


Bromide was lowest in winter (0.02 mg/L) and highest in summer and fall (0.05- 
0.2 mg/L). The source water for plants 3 and 4 is a river, with intakes located 1.5 miles upstream 
of the confluence with another river. This area is influenced by the tides and is prone to flow 
reversal at the intakes. As much as 70 % of the source water can be contributed from the latter 
river, especially during low-flow conditions. Tidal influences were the source of bromide and 
should also have been a source of iodide. 

The source water was relatively low in alkalinity. The addition of coagulant and chlorine 
depressed the pH of this low-alkalinity water to 5.5-6.3. Raw-water ammonia ranged from 0.07 
to 0.12 mg/L as N. 

DBPs 


Tables 8-17 show results for the DBPs that were analyzed at the Metropolitan Water 
District of Southern California (MWDSC) for sampling periods 11/13/00, 2/5/01, 8/1/01, 
10/16/01, and 1/28/02. Tables 18 (2/5/01), 19 (10/16/01), and 20 (10/16/01) show results for 
additional target DBPs that were analyzed at the University of North Carolina (UNC), which 
include halofuranones. Table 21 shows results from broadscreen DBP analyses conducted at the 
U.S. Environmental Protection Agency (USEPA) for sampling periods 11/13/00, 8/1/01, and 
1/28/02. 


Summary of tables for halogenated organic and other nonhalogenated organic DBPs 


DBP Analyses (Laboratory) 

11/13/00 

2/5/01 

8/1/01 

10/16/01 

1/28/02 

Halogenated organic DBPs (MWDSC) 

Tables 8-9 

Tables 10-11 

Tables 12-13 

Tables 14-15 

Tables 16-17 

Additional target DBPs (UNC) 


Table 18 


Table 19 


Halogenated ftiranones (UNC) 




Table 20 


Broadscreen analysis (USEPA) 

Table 21 


Table 21 


Table 21 


220 






















Table 8. DBP results at plant 3 (11/13/00) 


11/13/2000 

MRL a 

Plant 3 b 

Compound 

pg/L 

Raw 

Rapid Mix 

GAC Inf 

GAC Eff 

Plant Eff 

SDS/Ave 

SDS/Max 

DS/Ave 

DS/Max 

Halomethanes 











Chloromethane 

0.15 

ND d 


ND 

ND 

ND 

ND 


ND 


Bromomethane 

0.20 

ND 


ND 

ND 

ND 

ND 


ND 


Bromochloromethane 

0.14 

ND 


ND 

ND 

ND 

ND 


ND 


Dibromomethane 

0.11 

ND 


ND 

ND 

ND 

ND 


ND 


Chloroform 6 

0.10 

0.7 

5 

7 

9 

12 

16 

20 

14 

18 

Bromodichloromethane 6 

0.10 

0.7 

4 

9 

9 

13 

17 

19 

15 

19 

Dibromochloromethane 6 

0.12 

0.3 

1 

3 

2 

5 

7 

8 

6 

7 

Bromoform 6 

0.10 

ND 

0.7 

0.8 

0.4 

0.7 

1 

1 

0.8 

1 

THM4 f 


2 

11 

20 

20 

31 

41 

48 

36 

45 

Dichloroiodomethane 

0.10 

ND 

NR 9 

2 

1 

2 

2 

NR 

2 

NR 

Bromochloroiodomethane 

0.50 

ND 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

Dibromoiodomethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.59 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.53 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.22 

ND 

0.7 

ND 

ND 

0.5 

0.6 

0.9 

0.9 

0.4 

Carbon tetrachloride 

0.06 

ND 


0.8 

0.3 

0.3 

0.3 


0.3 


Haloacetic acids 











Monochloroacetic acid 6 

2 



ND 

3.2 

ND 

4.2 


3.9 


Monobromoacetic acid 6 

1 



ND 

ND 

ND 

ND 


ND 


Dichloroacetic acid 6 

1 



12 

ND 

6.7 

6.9 


6.4 


Bromochloroacetic acid 6 

1 



7.1 

ND 

3.0 

3.1 


3.0 


Dibromoacetic acid 6 

1 



1.2 

ND 

1.0 

1.0 


ND 


Trichloroacetic acid 6 

1 



10 

ND 

6.0 

5.6 


5.6 


Bromodichloroacetic acid 

1 



3.3 

ND 

2.6 

2.5 


2.4 


Dibromochloroacetic acid 

1 



1.2 

ND 

1.1 

1.0 


1.1 


Tribromoacetic acid 

2 



ND 

ND 

ND 

ND 


ND 


HAA5 h 




24 

3.2 

14 

18 


16 


HAA9' 




36 

3.2 

20 

24 


22 


DXAA j 




21 

ND 

11 

11 


9.4 


TXAA k 




15 

ND 

9.7 

9.1 


9.1 


Haloacetonitriles 











Chloroacetonitrile 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile 6 

0.10 

ND 

0.5 

0.9 

0.2 

1 

2 

2 

1 

2 

Bromochloroacetonitrile 6 

0.10 

ND 

0.2 

0.3 

ND 

0.9 

1 

1 

0.8 

1 

Dibromoacetonitrile 6 

0.10 

ND 

ND 

ND 

ND 

0.3 

0.2 

0.3 

0.2 

0.2 

T richloroacetonitrile 6 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloketones 











Chloropropanone 

0.10 

ND 

0.2 

0.3 

ND 

ND 

0.3 

0.3 

0.1 

0.2 

1,1-Dichloropropanone 6 

0.10 

ND 

0.5 

1 

0.1 

0.5 

0.6 

0.6 

0.3 

0.5 

1,3-Dichloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

3 

ND 


ND 

ND 

ND 

ND 


ND 


1,1,1 -T richloropropanone 6 

0.10 

ND 

1 

1 

0.3 

0.9 

1 

1 

1 

1 

1,1,3-T richloropropanone 

0.10 

ND 

0.2 

0.2 

ND 

ND 

0.1 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

3 

ND 


<3‘ 

ND 

<3 

ND 


<3 


1,1,1 -T ribromopropanone 

3 

ND 


ND 

ND 

ND 

ND 


ND 


1,1,3-T ribromopropanone 

3 

ND 


ND 

ND 

ND 

ND 


ND 


1,1,3,3-T etrachloropropanone 

0.10 

ND 

0.2 

0.2 

ND 

0.2 

0.1 

0.1 

0.1 

0.1 

1,1,3,3-T etrabromopropanone 

0.10 

ND 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


221 





































































Table 8 (continued) 


11/13/2000 

MRL a 

Plant 3 b 

Compound 

mq/l 

Raw 

Rapid Mix 

GAC Inf 

GAC Eff 

Plant Eff 

SDS/Ave 

SDS/Max 

DS/Ave 

DS/Max 

Haloacetaldehydes 











Dichloroacetaldehyde 

0.16 

0.1 

0.8 

2 

0.2 

0.8 

1 

1 

0.6 

2 

Brornochloroacetaldehyde m 
Chloral hydrate e m 

0.20 

ND 

0.8 

4 

ND 

2 

4 

4 

2 

4 

Tribromoacetaldehyde 

0.10 

ND 

0.2 

0.2 

ND 

ND 

0.1 

0.2 

ND 

ND 

Halonitromethanes 











Bromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

3 

ND 


ND 

ND 

ND 

ND 


Kin 

1 1 L/ 


Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 6 

0.10 

ND 

ND 

0.1 

ND 

ND 

ND 

0.1 

ND 

0.2 

Miscellaneous ComDOunds 











Methyl ethyl ketone 

1.90 

ND 


ND 

ND 

ND 

ND 


ND 


Methyl tertiary butyl ether 

0.16 

1.0 


1.0 

1.0 

1.1 

1.0 


1.1 


Benzyl chloride 

0.50 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

NR 


a MRL = Minimum reporting level, which equals method detection limit (MDL) 
or lowest calibration standard or concentration of blank 

b Plant 3 sampled at (1) raw water, (2) effluent of rapid mix, (3) GAC influent and (4) effluent, 

(5) plant effluent, (6) SDS testing of plant effluent held for average detention time and (7) held for maximum detention time, 
(8) DS at average detention time and (9) at maximum detention time. 

c Plant 4 sampled at (1) GAC influent and (2) effluent, (3) plant effluent, 

(4) SDS testing of plant effluent held for average detention time and (5) held for maximum detention time, 

(6) DS at average detention time and (7) at maximum detention time. 
d ND = Not detected at or above MRL 

e DBP in the Information Collection Rule (ICR) (note: some utilities collected data for all 9 
haloacetic acids for the ICR, but monitoring for only 6 haloacetic acids was required) 
f THM4 = Sum of 4 THMs (chloroform, bromodichloromethane, dibromochloromethane, bromoform) 

9 NR = Not reported, due to interference problem on gas chromatograph or to problem with quality assurance 
h HAA5 = Sum of 5 haloacetic acids (monochloro-, monobromo-, dichloro-, dibromo-, trichloroacetic acid) 

'HAA9 = Sum of 9 haloacetic acids 

J DXAA = Sum of dihaloacetic acids (dichloro-, bromochloro-, dibromoacetic acid) 

k 

TXAA = Sum of trihaloacetic acids (trichloro-, bromodichloro-, dibromochoro-, tribromoacetic acid) 

'<3: Concentration less than MRL of 3 pg/L 

m Bromochloroacetaldehyde and chloral hydrate co-eulte; result = sum of 2 DBPs 


222 






























Table 9. DBP results at plant 4 (11/13/00) 


11/13/2000 

MRL a 

Plant 4 C 

Compound 

mq/l 

GAC Inf 

GAC Eff 

Plant Eff 

SDS/Ave 

SDS/Max 

DS/Ave 

DS/Max 

Halomethanes 









Chloromethane 

0.15 

ND 

ND 

ND 

ND 


ND 


Bromomethane 

0.20 

ND 

ND 

ND 

ND 


ND 


Bromochloromethane 

0.14 

ND 

ND 

ND 

ND 


ND 


Dibromomethane 

0.11 

ND 

ND 

ND 

ND 


ND 


Chloroform® 

0.10 

30 

33 

43 

56 

61 

41 

46 

Bromodichloromethane® 

0.10 

17 

21 

28 

33 

37 

24 

27 

Dibromochloromethane® 

0.12 

5 

6 

7 

7 

8 

6 

7 

Bromoform® 

0.10 

1 

1 

1 

0.9 

0.9 

1 

0.9 

THM4 f 


53 

61 

79 

97 

107 

72 

81 

Dichloroiodomethane 

0.10 

1 

1 

1 

1 

NR 

1 

NR 

Bromochloroiodomethane 

0.50 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

Dibromoiodomethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.59 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.53 

ND 

0.6 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.22 

0.5 

0.3 

2 

2 

2 

2 

2 

Carbon tetrachloride 

0.06 

0.3 

0.4 

0.8 

0.7 


0.7 


Haloacetic acids 









Monochloroacetic acid® 

2 

7.7 

12 

6.4 

11 


5.1 


Monobromoacetic acid® 

1 

1.0 

ND 

ND 

1.5 


ND 


Dichloroacetic acid® 

1 

24 

23 

27 

30 


22 


Bromochloroacetic acid® 

1 

7.0 

6.4 

8.0 

9.4 


5.9 


Dibromoacetic acid® 

1 

1.0 

ND 

1.0 

1.2 


ND 


Trichloroacetic acid® 

1 

27 

27 

32 

34 


24 


Bromodichloroacetic acid 

1 

11 

11 

13 

14 


9.7 


Dibromochloroacetic acid 

1 

1.7 

1.7 

2.0 

2.3 


1.6 


Tribromoacetic acid 

2 

ND 

ND 

ND 

ND 


ND 


HAA5 h 


61 

61 

66 

78 


52 


HAA9' 


81 

81 

89 

103 


69 


DXAA j 


32 

29 

36 

41 


28 


TXAA k 


40 

40 

46 

50 


36 


Haloacetonitriles 









Chloroacetonitrile 

0.10 

ND 

ND 

0.1 

0.1 

0.1 

ND 

0.1 

Bromoacetonitrile 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile® 

0.10 

5 

5 

5 

5 

6 

5 

5 

Bromochloroacetonitrile® 

0.10 

1 

1 

1 

2 

2 

1 

1 

Dibromoacetonitrile® 

0.10 

0.1 

0.1 

0.2 

0.2 

0.2 

0.1 

0.1 

T richloroacetonitrile® 

0.10 

0.2 

0.2 

0.1 

ND 

ND 

0.1 

0.1 

Haloketones 









Chloropropanone 

0.10 

0.4 

0.5 

0.3 

0.2 

0.2 

0.2 

0.3 

1,1-Dichloropropanone® 

0.10 

1 

1 

0.9 

0.3 

0.3 

1 

0.8 

1,3-Dichloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

3 

ND 

ND 

ND 

ND 


ND 


1,1,1 -T richloropropanone® 

0.10 

5 

5 

5 

6 

7 

5 

5 

1,1,3-T richloropropanone 

0.10 

0.3 

0.3 

0.2 

0.2 

0.2 

0.4 

0.3 

1 -Bromo-1,1 -dichloropropanone 

3 

<3 

<3 

<3 

<3 


<3 


1,1,1 -T ribromopropanone 

3 

ND 

ND 

ND 

ND 


ND 


1,1,3-T ribromopropanone 

3 

ND 

ND 

ND 

ND 


ND 


1,1,3,3-Tetrachloropropanone 

0.10 

0.6 

0.8 

0.4 

0.4 

0.4 

0.7 

0.4 

1,1,3,3-T etrabromopropanone 

0.10 

0.3 

0.2 

0.1 

0.3 

0.3 

0.2 

0.2 


223 




































































Table 9 (continued) 


11/13/2000 

MRL a 

Plant 4 C 

Compound 

MQ/L 

GAC Inf 

GAC Eff 

Plant Eff 

SDS/Ave 

SDS/Max 

DS/Ave 

DS/Max 

Haloacetaldehydes 









Dichloroacetaldehyde 

0.16 

4 

5 

3 

2 

3 

3 

3 

Bromochloroacetaldehyde" 1 
Chloral hydrate 6 ’" 1 

0.20 

12 

13 

14 

18 

22 

15 

15 

T ribromoacetaldehyde 

0.10 

0.1 

0.1 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 









Bromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

3 

ND 

ND 

ND 

ND 


ND 


Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 6 

0.10 

0.2 

0.2 

0.2 

0.2 

0.3 

0.2 

0.2 

Miscellaneous Compounds 









Methyl ethyl ketone 

1.90 

ND 

ND 

ND 

ND 


ND 


Methyl tertiary butyl ether 

0.16 

0.8 

0.8 

0.8 

0.9 


0.9 


Benzyl chloride 

0.50 

NR 

NR 

NR 

NR 

NR 

NR 

NR 


224 





























Table 10. DBP results at plant 3 (2/5/01) 


02/05/2001 

MRL a 

Plant 3 b 

Compound 

pg/L 

Raw 

Rapid Mix 

GAC Inf 

GAC Eff 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

S DS/Max 

Halomethanes 











Chloromethane 

0.15 

ND d 


ND 

ND 

ND 

ND 


ND 


Bromomethane 

0.20 

ND 


ND 

ND 

ND 

ND 


ND 


Bromochloromethane 

0.14 

ND 


ND 

ND 

ND 

ND 


ND 


Dibromomethane 

0.11 

ND 


ND 

ND 

ND 

ND 


ND 


Chloroform 6 

0.1 

0.5 

5.5 

15 

21 

27 

33 

37 

33 

40 

Bromodichloromethane 6 

0.1 

ND 

1.0 

3.1 

3.7 

5.3 

5.9 

6.0 

5.8 

6.4 

Dibromochloromethane 6 

0.10 

ND 

ND 

0.4 

0.6 

0.8 

0.8 

0.9 

0.9 

0.9 

Bromoform 6 

0.12 

ND 

ND 

ND 

0.1 

0.1 

0.3 

0.3 

0.3 

0.3 

THM4* 


0.5 

6.5 

18 

25 

33 

40 

44 

40 

48 

Dichloroiodomethane 

0.25 

ND 

NR 9 

0.29 

0.27 

0.30 

0.31 

NR 

0.26 

NR 

Bromochloroiodomethane 

0.20 

ND 

NR 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

Dibromoiodomethane 

0.60 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.51 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.56 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.54 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 

ND 


ND 

ND 

ND 

ND 


ND 


T ribromochloromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 











Monochloroacetic acid 6 

2 



3.6 

ND 

2.3 

2.8 


2.6 


Monobromoacetic acid 6 

1 



ND 

ND 

ND 

ND 


ND 


Dichloroacetic acid 6 

1 



25 

4.2 

11 

12 


11 


Bromochloroacetic acid 6 

1 



1.7 

ND 

1.2 

1.2 


1.2 


Dibromoacetic acid 6 

1 



ND 

ND 

ND 

ND 


ND 


Trichloroacetic acid 6 

1 



28 

15 

19 

21 


19 


Bromodichloroacetic acid 

1 



2.4 

1.3 

1.9 

1.9 


1.8 


Dibromochloroacetic acid 

1 



ND 

ND 

ND 

ND 


ND 


Tribromoacetic acid 

2 



ND 

ND 

ND 

ND 


ND 


HAA5 h 




57 

19 

32 

36 


33 


HAA9' 




61 

21 

35 

39 


36 


DXAA j 




27 

4.2 

12 

13 


12 


TXAA k 




30 

16 

21 

23 


21 


Haloacetonitriles 











Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile 6 

0.10 

ND 

0.6 

2.4 

1.6 

2.2 

2.4 

2.4 

2.4 

2.5 

Bromochloroacetonitrile 6 

0.1 

ND 

ND 

0.2 

ND 

0.2 

0.2 

0.2 

0.2 

0.3 

Dibromoacetonitrile 6 

0.17 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

T richloroacetonitrile 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloketones 











Chloropropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dichloropropanone 6 

0.11 

ND 

1.1 

0.9 

0.5 

0.6 

1.0 

1.1 

1.1 

1.2 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

N/A n 

NR 


NR 

NR 

NR 

NR 


NR 


1,3-Dibromopropanone 

N/A 

NR 


NR 

NR 

NR 

NR 


NR 


1,1,1 -T richloropropanone 6 

0.10 

ND 

1.6 

3.1 

2.4 

2.5 

2.7 

2.6 

2.4 

2.4 

1,1,3-T richloropropanone 

0.10 

ND 

0.3 

0.2 

0.2 

0.2 

0.2 

0.2 

ND 

0.2 

1 -Bromo-1,1 -dichloropropanone 

N/A 

NR 


NR 

NR 

NR 

NR 


NR 


1,1,1 -T ribromopropanone 

N/A 

NR 


NR 

NR 

NR 

NR 


NR 


1,1,3-T ribromopropanone 

N/A 

NR 


NR 

NR 

NR 

NR 


NR 


1,1,3,3-T etrachloropropanone 

0.12 

ND 

0.4 

0.7 

0.5 

0.4 

0.6 

0.4 

0.2 

0.4 

1,1,1,3-T etrachloropropanone 

N/A 

NR 


NR 

NR 

NR 

NR 


NR 


1,1,3,3-T etrabromopropanone 

0.58 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


225 








































































Table 10 (continued) 


02/05/2001 

"mrl* 

pg/L 

Plan" 3 b 

Compound 

Raw 

Rapid Mix 

GAC Inf 

GAC Eff 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Haloacetaldehydes 











Dichloroacetaldehyde 

0.16 

ND 

0.8 

2 

1 

1 

1 

1 

2 

2 

Bromochloroacetaldehyde 

0.1 

ND 

ND 

0.1 

0.1 

0.1 

0.1 

0.1 

0.1 

0.1 

Chloral hydrate® 

0.1 

ND 

1.0 

3.0 

1.8 

2.7 

3.8 

3.6 

3.4 

3.6 

T ribromoacetaldehyde 

0.1 

ND 

0.2 

0.2 

0.1 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 











Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

N/A 

NR 


NR 

NR 

NR 

NR 


NR 


Bromochloronitromethane 

N/A 

NR 


NR 

NR 

NR 

NR 


NR 


Dibromonitromethane 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin® 

0.1 

ND 

0.4 

0.8 

0.2 

0.3 

0.4 

0.5 

0.5 

0.6 

Miscellaneous Compounds 











Methyl ethyl ketone 

1.9 

ND 


ND 

ND 

ND 

ND 


ND 


Methyl tertiary butyl ether 

0.16 

0.4 


0.5 

0.5 

0.4 

0.5 


0.4 


Benzyl chloride 

2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


n N/A = Not applicable 


226 
































Table 11. DBP results at 
02/05/2001 


plant 4 (2/5/01) 

mrl7 


Plant 4 C 


Compound 

mq/l 

GAC Inf 

GAC Eff 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Halomethanes 









Chloromethane 

0.15 

ND 

ND 

ND 

ND 


ND 


Bromomethane 

0.20 

ND 

ND 

ND 

ND 


ND 


Bromochloromethane 

0.14 

ND 

ND 

ND 

ND 


ND 


Dibromomethane 

0.11 

ND 

ND 

ND 

ND 


ND 


Chloroform 6 

0.1 

24 

27 

29 

33 

33 

36 

42 

Bromodichloromethane 6 

0.1 

3.3 

3.8 

4.3 

4.7 

4.7 

5.3 

6.1 

Dibromochloromethane 6 

0.10 

0.5 

0.5 

0.7 

0.7 

0.7 

0.8 

0.9 

Bromoform 6 

0.12 

0.1 

ND 

0.1 

0.1 

0.3 

0.1 

ND 

THM4 f 


28 

31 

34 

39 

38 

42 

49 

Dichloroiodomethane 

0.25 

0.27 

0.25 

0.29 

0.28 

NR 

0.29 

NR 

Bromochloroiodomethane 

0.20 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

Dibromoiodomethane 

0.60 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.51 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.56 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.54 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 

ND 

ND 

ND 

ND 


ND 


T ribromochloromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic adds 









Monochloroacetic acid 6 

2 

5.1 

5.5 

4.7 

5.7 


6.3 


Monobromoacetic acid 6 

1 

ND 

ND 

ND 

ND 


ND 


Dichloroacetic acid 6 

1 

32 

31 

25 

25 


28 


Bromochloroacetic acid 6 

1 

1.9 

1.9 

1.7 

1.7 


1.9 


Dibromoacetic acid 6 

1 

ND 

ND 

ND 

ND 


ND 


Trichloroacetic acid 6 

1 

33 

35 

35 

35 


38 


Bromodichloroacetic acid 

1 

3.5 

3.6 

3.3 

3.6 


4.6 


Dibromochloroacetic acid 

1 

1.0 

1.0 

ND 

ND 


ND 


Tribromoacetic acid 

2 

ND 

ND 

ND 

ND 


ND 


HAA5 h 


70 

72 

65 

66 


72 


HAA9' 


77 

78 

70 

71 


79 


DXAA' 


34 

33 

27 

27 


30 


TXAA k 


38 

40 

38 

39 


43 


Halnacfitnnitrilos 









Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile 6 

0.10 

2.6 

2.8 

2.7 

2.8 

2.8 

3.2 

3.4 

Bromochloroacetonitrile 6 

0.1 

0.2 

0.2 

0.2 

0.3 

0.3 

0.3 

0.4 

Dibromoacetonitrile 6 

0.17 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

T richloroacetonitrile 6 

0.1 

0.1 

0.1 

0.1 

0.1 

0.1 

0.1 

0.1 

Haloketones 









Chloropropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dichloropropanone 6 

0.11 

1.0 

1.0 

0.9 

1.0 

1.0 

1.0 

1.0 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

N/A 

NR 

NR 

NR 

NR 


NR 


1,3-Dibromopropanone 

N/A 

NR 

NR 

NR 

NR 


NR 


1,1,1 -T richloropropanone 6 

0.10 

3.2 

3.3 

3.1 

3.2 

3.3 

3.7 

4.0 

1,1,3-T richloropropanone 

0.10 

0.3 

0.3 

0.2 

0.3 

0.2 

0.3 

0.2 

1 -Bromo-1,1 -dichloropropanone 

N/A 

NR 

NR 

NR 

NR 


NR 


1,1,1 -T ribromopropanone 

N/A 

NR 

NR 

NR 

NR 


NR 


1,1,3-T ribromopropanone 

N/A 

NR 

NR 

NR 

NR 


NR 


1,1,3,3-Tetrachloropropanone 

0.12 

0.5 

0.6 

0.6 

0.5 

0.5 

0.6 

0.5 

1,1,1,3-Tetrachloropropanone 

N/A 

NR 

NR 

NR 

NR 


NR 


1,1,3,3-T etrabromopropanone 

0.58 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


227 







































































Table 11 (continued) 


02/05/2001 

■mrl 7 

Mg/L 

Plant 4 C 

Compound 

GAC Inf 

GAC Eff 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloacetaldehvdes 









Dichloroacetaldehyde 

0.16 

2 

3 

2 

2 

2 

2 

2 

Bromochloroacetaldehyde 

0.1 

0.1 

0.1 

0.1 

0.1 

0.1 

0.1 

0.1 

Chloral hydrate 6 

0.1 

3.2 

3.6 

4.5 

4.4 

4.7 

6.9 

7.5 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 









Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

N/A 

NR 

NR 

NR 

NR 


NR 


Bromochloronitromethane 

N/A 

NR 

NR 

NR 

NR 


NR 


Dibromonitromethane 

0.12 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 6 

0.1 

0.8 

0.8 

0.6 

0.6 

0.6 

0.7 

0.7 

Miscellaneous Compounds 









Methyl ethyl ketone 

1.9 

ND 

ND 

ND 

ND 


ND 


Methyl tertiary butyl ether 

0.16 

0.5 

0.4 

0.5 

0.5 


0.5 


Benzyl chloride 

2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


228 

































Table 12. DBP results at 
08 / 01/2001 


)lant 3 (8/1/01) _ 

MRL d | Plant 3 b 


Compound 

pg/L 

Raw 

Rapid Mix 

GAC Inf 

GAC Eff 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Halomethanes 











Chloromethane 

0.2 

ND d 


0.3 

ND 

ND 

ND 


ND 


Bromomethane 

0.2 

ND 


ND 

ND 

ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 


ND 

ND 

ND 

ND 


ND 


Dibromomethane 

0.5 

ND 


ND 

ND 

ND 

ND 


ND 


Chloroform 6 

0.1 

0.2 

3 

8 

14 

16 

19 

18 

19 

NR 9 

Bromodichloromethane 6 

0.1 

0.1 

0.9 

4 

5 

7 

8 

7 

8 

NR 

Dibromochloromethane 6 

0.1 

ND 

0.2 

0.8 

0.6 

2 

2 

2 

2 

NR 

Bromoform 6 

0.11 

ND 

ND 

ND 

ND 

0.3 

0.3 

0.2 

0.4 

0.5 

THM4' 


0.3 

4.1 

13 

20 

25 

28 

27 

29 

NR 

Dichloroiodomethane 

0.5 

ND 

NR 

<0.5° 

ND 

ND 

ND 

ND 

ND 

NR 

Bromochloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromoiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 

ND 


ND 

ND 

ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetio arid.'; 











Monochloroacetic acid 6 

2 



3.9 

ND 

2.2 

ND 


2.3 


Monobromoacetic acid 6 

1 



1.2 

ND 

ND 

ND 


ND 


Dichloroacetic acid 6 

1 



25 

ND 

6.4 

8.7 


7.3 


Bromochloroacetic acid 6 

1 



6.5 

1.6 

2.7 

3.2 


3.1 


Dibromoacetic acid 6 

1 



1.1 

ND 

1.0 

1.0 


ND 


Trichloroacetic acid 6 

1 



16 

ND 

2.2 

2.3 


2.2 


Bromodichloroacetic acid 

1 



4.6 

ND 

1.5 

1.4 


1.4 


Dibromochloroacetic acid 

1 



1.2 

ND 

ND 

ND 


ND 


Tribromoacetic acid 

2 



ND 

ND 

ND 

ND 


ND 


HAA5 h 




47 

ND 

12 

12 


12 


HAA9' 




60 

2 

16 

17 


16 


DXAA j 




33 

2 

10 

13 


10 


TXAA K 




22 

ND 

3.7 

3.7 


3.6 


Haloacetonitriles 











Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile 6 

0.10 

ND 

0.6 

4 

0.1 

0.9 

1 

1 

2 

2 

Bromochloroacetonitrile 6 

0.1 

ND 

0.1 

0.8 

ND 

0.7 

0.8 

0.8 

0.9 

1 

Dibromoacetonitrile 6 

0.14 

ND 

ND 

0.2 

ND 

0.6 

0.7 

0.5 

0.8 

0.8 

Trichloroacetonitrile 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 


ND 

ND 

ND 





Dibromochloroacetonitrile 

0.5 

ND 


ND 

ND 

ND 





T ribromoacetonitrile 

0.5 

ND 


ND 

ND 

ND 





Haloketones 











Chloropropanone 

0.1 

ND 

ND 

0.1 

0.1 

0.1 

0.1 

0.1 

0.3 

0.3 

1,1 -Dichloropropanone 6 

0.10 

ND 

0.9 

2 

0.2 

0.4 

1 

1 

0.8 

1 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1-Trichloropropanone 6 

0.1 

ND 

1 

2 

0.2 

0.8 

0.5 

0.2 

0.8 

0.4 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

0.1 

ND 

ND 

0.5 

ND 

0.2 

ND 

ND 

ND 

ND 

1,1,1 -T ribromopropanone 

0.29 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-Tribromopropanone 

0.14 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrachloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-T etrachloropropanone 

0.10 

ND 

ND 

2 P 

1 p 

0.6 P 

ND 

ND 

ND 

ND 

1,1,3,3-T etrabromopropanone 

0.1 

ND 

ND 

0.1 

0.2 

0.3 

ND 

ND 

ND 

ND 


229 













































































Table 12 (continued) 


08/01/2001 

MRL 3 

mq/l 

Plant 3 b 

Compound 

Raw 

Rapid Mix 

GAC Inf 

GAC Eff 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloacetaldehydes 











Dichloroacetaldehyde 

0.1 

ND 

0.8 

4 

0.9 

1 

3 

3 

2 

4 

Bromochloroacetaldehyde 

0.1 

ND 

ND 

2 

ND 

ND 

0.5 

ND 

0.4 

0.5 

Chloral hydrate 6 

0.1 

ND 

ND 

3 P 

0.6 P 

2 P 

2 P 

2 P 

2 P 

2 P 

T ribromoacetaldehyde 

0.1 

ND 

ND 

1 p 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 











Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloronitromethane 

0.5 

ND 


ND 

ND 

ND 





Dibromochloronitromethane 

0.5 

ND 


ND 

ND 

ND 





Bromopicrin 

2.0 

ND 


ND 

ND 

ND 





Miscellaneous Compounds 











Methyl ethyl ketone 

0.5 

28 


12 

15 

5 

5 


2 


Methyl tertiary butyl ether 

0.2 

1 


1 

1 

1 

1 


0.9 


1,1,2,2-Tetrabromo-2-chloroethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Benzyl chloride 

0.25 

ND 

NR 

ND 

ND 

ND 

ND 

NR 

ND 

NR 


°<0.5: Detected by SPE-GC/MS, but below MRL for SPE-GC/MS 

p Low spike recoveries for 1,1,1,3- and 1,1,3,3-tetrachloropropanone and for chloral hydrate and tribromoacetaldehyde. 


230 





































Table 13. DBP results at plant 4 (8/1/01) 


08/01/2001 

"mrlT 

Plant 4 C 

Compound 

mq/l 

GAC Inf 

GAC Eff 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Halomethanes 









Chloromethane 

0.2 

ND 

ND 

ND 

ND 


ND 


Bromomethane 

0.2 

ND 

ND 

ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 

ND 

ND 

ND 


ND 


Dibromomethane 

0.5 

ND 

ND 

ND 

ND 


ND 


Chloroform® 

0.1 

22 

27 

22 

27 

27 

27 

25 

Bromodichloromethane® 

0.1 

7 

9 

8 

9 

10 

9 

9 

Dibromochloromethane® 

0.1 

1 

1 

1 

1 

2 

2 

2 

Bromoform® 

0.11 

ND 

ND 

ND 

ND 

ND 

ND 

0.1 

THM4 f 


30 

37 

31 

38 

39 

38 

36 

Dichloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

NR 

0.5 

NR 

Bromochloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromoiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 

ND 

ND 

ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 









Monochloroacetic acid® 

2 

20 

16 

8.2 

7.8 


8.1 


Monobromoacetic acid® 

1 

ND 

ND 

ND 

ND 


ND 


Dichloroacetic acid® 

1 

56 

25 

24 

25 


26 


Bromochloroacetic acid® 

1 

8.7 

4.5 

4.5 

4.9 


5.1 


Dibromoacetic acid® 

1 

ND 

ND 

ND 

ND 


ND 


Trichloroacetic acid® 

1 

68 

49 

29 

31 


30 


Bromodichloroacetic acid 

1 

12 

8.7 

6.8 

7.3 


7.0 


Dibromochloroacetic acid 

1 

1.9 

1.3 

1.3 

1.2 


1.2 


Tribromoacetic acid 

2 

ND 

ND 

ND 

ND 


ND 


HAA5 h 


144 

90 

61 

64 


64 


HAA9' 


167 

105 

74 

77 


77 


DXAA j 


65 

30 

29 

30 


31 


TXAA K 


82 

59 

37 

40 


38 


Haloacetonitriles 









Chloroacetonitrile 

0.1 

0.3 

0.4 

0.3 

0.3 

0.3 

0.3 

0.3 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile® 

0.10 

10 

10 

6 

8 

8 

8 

8 

Bromochloroacetonitrile® 

0.1 

1 

1 

1 

1 

1 

1 

1 

Dibromoacetonitrile® 

0.14 

0.8 

0.3 

0.4 

0.4 

0.5 

0.4 

0.4 

T richloroacetonitrile® 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 

ND 

ND 




ND 

Dibromochloroacetonitrile 

0.5 

ND 

ND 

ND 




ND 

Tribromoacetonitrile 

0.5 

ND 

ND 

ND 




ND 

Haloketones 









Chloropropanone 

0.1 

0.1 

0.2 

0.1 

0.2 

0.2 

0.2 

0.2 

1,1-Dichloropropanone® 

0.10 

3 

2 

0.9 

1 

0.8 

0.8 

1 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T richloropropanone® 

0.1 

8 

7 

4 

6 

6 

6 

5 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

0.1 

0.7 

0.7 

0.4 

0.5 

0.4 

0.3 

0.1 

1,1,1 -T ribromopropanone 

0.29 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-Tribromopropanone 

0.14 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrachloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-T etrachloropropanone 

0.10 

2 P 

1 p 

0.7 p 

1 p 

ND 

0.7 p 

0.2 P 

1,1,3,3-T etrabromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


231 








































































Table 13 (continued) 


08/01/2001 

MRi? 

mq/l 

Plant 4 C 

Compound 

GAC Inf 

GAC Eff 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloacetaldehvdes 









Dichloroacetaldehyde 

0.1 

8 

4 

3 

3 

3 

5 

5 

Bromochloroacetaldehyde 

0.1 

2 

0.4 

0.4 

0.3 

0.3 

0.3 

0.4 

Chloral hydrate 6 

0.1 

16 p 

6 P 

6 P 

4 P 

4 P 

7 P 

11 p 

T ribromoacetaldehyde 

0.1 

2 P 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 









Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 6 

0.1 

ND 

ND 

ND 

ND 

ND 

0.2 

0.2 

Bromodichloronitromethane 

0.5 

ND 

ND 

ND 




ND 

Dibromochloronitromethane 

0.5 

ND 

ND 

ND 




ND 

Bromopicrin 

2.0 

ND 

ND 

ND 




ND 

Miscellaneous Compounds 









Methyl ethyl ketone 

0.5 

24 

23 

ND 

0.5 


0.6 


Methyl tertiary butyl ether 

0.2 

2 

2 

1 

1 


0.9 


1,1,2,2-Tetrabromo-2-chloroethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Benzyl chloride 

0.25 

ND 

ND 

ND 

ND 

NR 

ND 

NR 


e DBP in the Information Collection Rule (ICR) (note: some utilities collected 
haloacetic acids for the ICR, but monitoring for only 6 haloacetic acids was 
p Low spike recoveries for 1,1,1,3- and 1,1,3,3-tetrachloropropanone and for 


data for all 9 
required) 

chloral hydrate and tribromoacetaldehyde. 


232 





































Table 14. DBP results at plant 3 (10/16/01) 


10/16/2001 

MRL 3 

pg/L 

Plant 3* 

Compound 

Raw 

Rapid Mix 

GAC Inf 

GAC Eff 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Halomethanes 











Chloromethane 

0.2 

ND d 


ND 

ND 

ND 

ND 


ND 


Bromomethane 

0.2 

ND 


ND 

ND 

ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 


ND 

ND 

ND 

ND 


ND 


Dibromomethane 

0.5 

ND 


ND 

ND 

ND 

ND 


ND 


Chloroform 6 

0.1 

ND 

1 

8 

12 

18 

19 

20 

16 

23 

Bromodichloromethane 6 

0.1 

0.2 

2 

13 

14 

24 

26 

27 

24 

36 

Dibromochloromethane 6 

0.1 

ND 

0.8 

7 

6 

11 

12 

14 

10 

22 

Bromoform 6 

0.25 

ND 

0.2 

2 

0.8 

2 

3 

2 

4 

3 

THM4 f 


0.2 

4 

30 

33 

55 

60 

63 

54 

84 

Dichloroiodomethane 

0.5 

ND 

NR 9 

ND 

ND 

ND 

0.8 

NR 

0.5 

NR 

Bromochloroiodomethane 

0.5 

ND 

NR 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

Dibromoiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

NR 

Carbon tetrachloride 

0.2 

ND 


ND 

ND 

ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic adds 











Monochloroacetic acid 6 

2 



ND 

ND 

ND 

ND 


ND 


Monobromoacetic acid 6 

1 



ND 

ND 

ND 

ND 


ND 


Dichloroacetic acid 6 

1 



14 

ND 

4.6 

4.7 


3.4 


Bromochloroacetic acid 6 

1 



7.8 

ND 

3.4 

3.6 


4.2 


Dibromoacetic acid 6 

1 



3.5 

ND 

2.6 

2.6 


3.0 


Trichloroacetic acid 6 

1 



9.8 

ND 

1.2 

1.4 


1.4 


Bromodichloroacetic acid 

1 



8.2 

ND 

3.3 

3.4 


2.4 


Dibromochloroacetic acid 

1 



3.2 

ND 

2.0 

2.1 


1.7 


Tribromoacetic acid 

2 



ND 

ND 

ND 

ND 


ND 


HAA5 h 




27 

ND 

8.4 

8.7 


7.8 


HAA9' 




47 

ND 

17 

18 


16 


DXAA j 




25 

ND 

11 

11 


11 


TXAA K 




21 

ND 

6.5 

6.9 


5.5 


Haloacetonitriles 











Chloroacetonitrile 

0.2 

ND 

NR 

0.5 

ND 

0.3 

0.4 

NR 

0.4 

NR 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile 6 

0.1 

ND 

0.5 

2 

0.2 

0.7 

0.8 

0.9 

1 

2 

Bromochloroacetonitrile 6 

0.1 

ND 

0.4 

2 

ND 

1 

2 

2 

2 

2 

Dibromoacetonitrile 6 

0.1 

ND 

0.5 

2 

0.1 

0.7 

0.7 

0.8 

1 

1 

T richloroacetonitrile 6 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 


ND 

ND 

ND 





Dibromochloroacetonitrile 

0.5 

ND 


ND 

ND 

ND 





T ribromoacetonitrile 

0.90 

ND 


ND 

ND 

ND 





Haloketones 











Chloropropanone 

0.1 

ND 

0.3 

0.5 

0.4 

0.6 

0.5 

0.6 

0.4 

0.5 

1,1 -Dichloropropanone 6 

0.10 

ND 

0.7 

1 

0.2 

0.4 

0.4 

0.4 

0.3 

0.4 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

0.1 

ND 

ND 

0.4 

ND 

0.1 

ND 

0.1 

ND 

ND 

1,1,1 -T richloropropanone 6 

0.1 

ND 

0.6 

1 

0.2 

0.5 

0.5 

0.5 

0.2 

0.2 

1,1,3-Trichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

0.1 

ND 

0.5 

1 

ND 

0.4 

0.2 

0.1 

ND 

ND 

1,1,1 -T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrachloropropanone 

0.1 

ND 

0.5 

2 

ND 

0.4 

ND 

ND 

ND 

ND 

1,1,1,3-Tetrachloropropanone 

0.10 

ND 

ND 

0.4 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


233 











































































Table 14 (continued) 


10/16/2001 

MRL* 

pg/L 

Plant 3 b 

Compound 

Raw 

Rapid Mix 

GAC Inf 

GAC Eff 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloacetaldeh^des 











Dichloroacetaldehyde 

0.22 

ND 

0.9 

4 

0.2 

0.7 

1 

1 

1 

2 

Bromochloroacetaldehyde 

0.5 

ND 

ND 

2 

ND 

ND 

1 

1 

1 

2 

Chloral hydrate 6 

0.1 

ND 

0.3 

4 

0.3 

0.7 

1 

2 

0.7 

1 

T ribromoacetaldehyde 

0.1 

ND 

ND 

1 

ND 

ND 

0.1 

ND 

ND 

ND 

Halonitromethanes 











Chloronitromethane 

0.1 

ND 

0.2 

0.3 

ND 

ND 

ND 

0.1 

NR 

NR 

Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

0.2 

0.2 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 6 

0.1 

ND 

ND 

0.1 

ND 

ND 

ND 

ND 

ND 

0.2 

Bromodichloronitromethane 

0.5 

ND 


0.5 

ND 

ND 





Dibromochloronitromethane 

0.5 

ND 


0.6 

ND 

0.5 





Bromopicrin 

0.5 

ND 


ND 

ND 

ND 





Miscellaneous Compounds 











Methyl ethyl ketone 

0.5 

0.6 


3 

ND 

ND 

ND 


ND 


Methyl tertiary butyl ether 

0.2 

1 


1 

1 

1 

1 


0.9 


1,1,2,2-Tetrabromo-2-chloroethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Benzyl chloride 

0.25 

ND 

NR 

ND 

ND 

ND 

ND 

NR 

ND 

NR 


234 







































Table 15. DBP results at plant 4 (10/16/01) 


10/16/2001 

MRL U 

Plant 4 C 

Compound 

Mg/L 

GAC Inf 

GAC Eff 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Halomethanes 









Chloromethane 

0.2 

ND 

ND 

ND 

ND 


ND 


Bromomethane 

0.2 

ND 

ND 

ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 

ND 

ND 

ND 


ND 


Dibromomethane 

0.5 

ND 

ND 

ND 

ND 


ND 


Chloroform 6 

0.1 

26 

30 

34 

34 

48 

60 

69 

Bromodichloromethane 6 

0.1 

27 

32 

34 

36 

45 

64 

68 

Dibromochloromethane 6 

0.1 

10 

11 

13 

14 

18 

32 

37 

Bromoform 6 

0.25 

1 

1 

2 

2 

1 

3 

2 

THM4 f 


64 

74 

83 

86 

112 

159 

176 

Dichloroiodomethane 

0.5 

ND 

0.7 

0.8 

0.9 

NR 

1 

NR 

Bromochloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

Dibromoiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.1 

ND 

ND 

ND 

ND 

ND 

NR 

NR 

Carbon tetrachloride 

0.2 

ND 

ND 

ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 









Monochloroacetic acid 6 

2 

2.5 

ND 

ND 

ND 


2.3 


Monobromoacetic acid 6 

1 

1.2 

ND 

ND 

ND 


1.2 


Dichloroacetic acid 6 

1 

23 

14 

17 

17 


15 


Bromochloroacetic acid 6 

1 

15 

7.5 

7.2 

7.3 


12 


Dibromoacetic acid 6 

1 

3.3 

1.5 

2.8 

2.9 


4.1 


Trichloroacetic acid 6 

1 

25 

22 

20 

20 


17 


Bromodichloroacetic acid 

1 

18 

15 

12 

12 


12 


Dibromochloroacetic acid 

1 

5.5 

4.4 

3.8 

3.9 


4.3 


Tribromoacetic acid 

2 

ND 

ND 

ND 

ND 


ND 


HAA5 h 


55 

38 

40 

40 


40 


HAA9' 


94 

64 

63 

63 


68 


DXAA j 


41 

23 

27 

27 


31 


TXAA K 


49 

41 

36 

36 


33 


Haloacetonitriles 









Chloroacetonitrile 

0.2 

0.9 

0.9 

0.9 

0.9 

NR 

1 

NR 

Bromoacetonitrile 

0.1 

ND 

0.1 

0.2 

0.1 

0.1 

ND 

ND 

Dichloroacetonitrile 6 

0.1 

6 

6 

5 

5 

7 

8 

7 

Bromochloroacetonitrile 6 

0.1 

2 

2 

2 

2 

3 

4 

4 

Dibromoacetonitrile 6 

0.1 

2 

1 

0.6 

1 

0.9 

2 

2 

T richloroacetonitrile 6 

0.1 

0.1 

ND 

0.1 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 

ND 

ND 





Dibromochloroacetonitrile 

0.5 

ND 

ND 

ND 





Tribromoacetonitrile 

0.90 

ND 

ND 

ND 





Haloketones 









Chloropropanone 

0.1 

0.3 

0.3 

0.4 

0.4 

0.5 

0.3 

0.3 

1,1-Dichloropropanone 6 

0.1 

2 

2 

1 

1 

0.3 

0.3 

0.6 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

0.1 

0.2 

0.1 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T richloropropanone 6 

0.1 

3 

3 

3 

3 

3 

2 

1 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

0.1 

2 

1 

0.9 

1 

0.7 

ND 

ND 

1,1,1 -T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrachloropropanone 

0.1 

1 

0.4 

0.3 

0.3 

0.2 

ND 

ND 

1,1,1,3-T etrachloropropanone 

0.1 

0.2 

0.3 

0.1 

0.1 

0.1 

ND 

ND 

1,1,3,3-T etrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


235 








































































Table 15 (continued) 


10/16/2001 

MRL 3 

M9/L 

Plant 4 C 

Compound 

GAC Inf 

GAC Eff 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloacetaldehvdes 









Dichloroacetaldehyde 

0.22 

5 

5 

3 

4 

4 

2 

2 

Bromochloroacetaldehyde 

0.5 

2 

2 

1 

1 

2 

1 

1 

Chloral hydrate 6 

0.1 

9 

9 

7 

8 

12 

15 

8 

T ribromoacetaldehyde 

0.1 

0.1 

0.1 

ND 

ND 

0.1 

ND 

ND 

Halonitromethanes 









Chloronitromethane 

0.1 

0.4 

0.4 

0.2 

0.2 

ND 

NR 

NR 

Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

0.2 

0.2 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 6 

0.1 

0.1 

0.2 

0.2 

0.2 

0.2 

ND 

0.2 

Bromodichloronitromethane 

0.5 

ND 

ND 

ND 





Dibromochloronitromethane 

0.5 

ND 

ND 

ND 





Bromopicrin 

0.5 

ND 

ND 

ND 





Miscellaneous Compounds 









Methyl ethyl ketone 

0.5 

3 

2 

1 

2 


2 


Methyl tertiary butyl ether 

0.2 

0.8 

1 

1 

1 


1 


1,1,2,2-Tetrabromo-2-chloroethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Benzyl chloride 

0.25 

ND 

ND 

ND 

ND 

NR 

ND 

NR 


236 




































Table 16. DBP results at plant 3 (1/28/02) 


01/28/2002 

MRL 3 

Mg/L 

Plant 3 b 

Compound 

Raw 

Rapid Mix 

GAC Inf 

GAC Eff 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Halomethanes 











Chloromethane 

0.2 

ND d 


ND 

ND 

ND 

ND 


ND 


Bromomethane 

0.2 

ND 


ND 

ND 

ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 


ND 

ND 

ND 

ND 


ND 


Dibromomethane 

0.5 

ND 


ND 

ND 

ND 

ND 


ND 


Chloroform 6 

0.2 

ND 

NR 9 

20 

16 

20 9 

NR 

NR 

NR 

NR 

Bromodichloromethane 6 

0.2 

ND 

NR 

4 

6 

7 

8 

NR 

10 

NR 

Dibromochloromethane 6 

0.5 

ND 

NR 

2 

3 

4 

5 

NR 

4 

NR 

Bromoform 6 

0.5 

ND 

NR 

ND 

0.6 

0.6 

0.6 

NR 

0.7 

NR 

THM4' 


ND 

NR 

26 

26 

32 

NR 

NR 

NR 

NR 

Dichloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloroiodomethane 

0.5 

ND 

NR 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

Dibromoiodomethane 

0.5 

ND 

NR 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

ND 

Bromodiiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

ND 

Iodoform 

1.0 

ND 

NR 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

Carbon tetrachloride 

0.2 

ND 


ND 

ND 

ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 











Monochloroacetic acid 6 

2 



ND 

ND 

2.5 

2.8 


2.7 


Monobromoacetic acid 6 

1 



ND 

ND 

ND 

ND 


ND 


Dichloroacetic acid 6 

1 



19 

4.3 

7.8 

7.6 


9.3 


Bromochloroacetic acid 6 

1 



2.6 

ND 

1.6 

1.5 


5.2 


Dibromoacetic acid 6 

1 



ND 

ND 

ND 

ND 


ND 


Trichloroacetic acid 6 

1 



20 

9.8 

13 

12 


13 


Bromodichloroacetic acid 

1 



5.6 

2.7 

4.4 

4.0 


1.5 


Dibromochloroacetic acid 

1 



2.0 

1.2 

1.6 

1.4 


2.8 


Tribromoacetic acid 

2 



ND 

ND 

ND 

ND 


ND 


HAA5 h 




39 

14 

23 

22 


25 


HAA9' 




49 

18 

31 

29 


35 


DXAA j 




22 

4.3 

9.4 

9.1 


15 


TXAA K 




28 

14 

19 

17 


17 


Haloacetonitriles 











Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

ND 

Dichloroacetonitrile 6 

1 

ND 

NR 

3 

1 

1 

NR 

NR 

NR 

NR 

Bromochloroacetonitrile 6 

0.1 

ND 

NR 

0.5 

0.2 

0.3 

0.4 

NR 

1 

0.7 

Dibromoacetonitrile 6 

0.1 

ND 

ND 

ND 

ND 

<0.5° 

<0.5 

ND 

<0.5 

0.2 

T richloroacetonitrile 6 

0.5 

ND 

NR 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

Bromodichloroacetonitrile 

0.5 

ND 


ND 

ND 

ND 





Dibromochloroacetonitrile 

0.5 

ND 


ND 

ND 

ND 





T ribromoacetonitrile 

0.95 

ND 


ND 

ND 

ND 





Haloketones 











Chloropropanone 

0.1 

ND 

0.1 

0.3 

0.3 

0.3 

0.3 

0.4 

NR 

0.3 

1,1 -Dichloropropanone 6 

0.10 

ND 

0.4 

1 

0.7 

0.7 

0.6 

0.2 

1 

NR 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

ND 

1,1-Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

ND 

1,1,1 -T richloropropanone 6 

0.5 

ND 

ND 

2 

1 

1 

1 

NR 

1 

NR 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

ND 

1-Bromo-1,1-dichloropropanone 

1.0 

ND 

NR 

1 

ND 

ND 

<1 r 

NR 

ND 

NR 

1,1,1-Tribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

ND 

1,1,3-T ribromopropanone 

0.1 

0.1 

ND 

0.2 

0.1 

ND 

0.1 

ND 

NR 

0.1 

1,1,3,3-Tetrachloropropanone 

0.10 

ND 

ND 

0.2 

ND 

ND 

ND 

ND 

NR 

0.2 

1,1,1,3-T etrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

ND 

1,1,3,3-Tetrabromopropanone 

N/A 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

NR 


237 










































































Table 16 (continued) 


01/28/2002 

MRL J 

pg/L 

Plant 3 b 

Compound 

Raw 

Rapid Mix 

GAC Inf 

GAC Eff 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloacetaldeh^des 











Dichloroacetaldehyde 

0.98 

ND 

0.6 

3 

1 

ND 

ND 

ND 

NR 

3 

Bromochloroacetaldehyde 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

ND 

Chloral hydrate® 

0.1 

0.3 

0.2 

3 

0.8 

0.9 

0.9 

ND 

NR 

4 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

ND 

Halonitromethanes 











Chloronitromethane 

N/A 

ND 


ND 

ND 

ND 

ND 


ND 


Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

ND 

Dichloronitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

0.2 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 

ND 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin® 

0.1 

ND 

ND 

0.5 

ND 

ND 

ND 

ND 

<0.5 

1 

Bromodichloronitromethane 

0.5 

ND 


0.5 

ND 

0.6 





Dibromochloronitromethane 

0.5 

ND 


ND 

ND 

ND 





Bromopicrin 

0.5 

ND 


ND 

ND 

ND 





Miscellaneous Compounds 











Methyl ethyl ketone 

0.5 

ND 


ND 

ND 

ND 

ND 


ND 


Methyl tertiary butyl ether 

0.2 

0.6 


0.6 

0.6 

0.6 

0.7 


0.7 


1,1,2,2-Tetrabromo-2-chloroethane 

2.5 

ND 

NR 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

Benzyl chloride 

0.25 

ND 

NR 

ND 

ND 

ND 

ND 

NR 

ND 

NR 


q Results in italics tentative due to problems with quality assurance 
r <1: Detected by SPE-GC/MS, but below MRL for SPE-GC/MS 


238 










































Table 17. DBP results at plant 4 (1/28/02) 


01/28/2002 

MRL 3 

pg/L 

Plant 4 C 

Compound 

GAC Inf 

GAC Eff 

Plant Eff 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Halomethanes 









Chloromethane 

0.2 

ND 

ND 

ND 

ND 


ND 


Bromomethane 

0.2 

ND 

ND 

ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 

ND 

ND 

ND 


ND 


Dibromomethane 

0.5 

ND 

ND 

ND 

ND 


ND 


Chloroform® 

0.2 

20 

20 

20 

NR 

NR 

NR 

NR 

Bromodichloromethane® 

0.2 

9 

6 

8 

8 

NR 

11 

NR 

Dibromochloromethane® 

0.5 

3 

2 

3 

2 

NR 

5 

NR 

Bromoform® 

0.5 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

THM4 f 


32 

28 

31 

NR 

NR 

NR 

NR 

Dichloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

Dibromoiodomethane 

0.5 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

1.0 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

Carbon tetrachloride 

0.2 

ND 

ND 

ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 









Monochloroacetic acid® 

2 

2.3 

2.6 

ND 

ND 


2.5 


Monobromoacetic acid® 

1 

ND 

ND 

1.0 

ND 


ND 


Dichloroacetic acid® 

1 

21 

21 

17 

16 


19 


Bromochloroacetic acid® 

1 

3.3 

3.2 

2.6 

2.4 


3.5 


Dibromoacetic acid® 

1 

ND 

ND 

ND 

ND 


ND 


Trichloroacetic acid® 

1 

26 

28 

21 

21 


24 


Bromodichloroacetic acid 

1 

6.8 

6.9 

5.8 

5.8 


5.3 


Dibromochloroacetic acid 

1 

2.8 

2.5 

1.9 

1.8 


ND 


Tribromoacetic acid 

2 

ND 

ND 

ND 

ND 


ND 


HAA5 h 


49 

52 

39 

37 


46 


HAA9 1 


62 

64 

49 

47 


54 


DXAA j 


24 

24 

20 

18 


23 


TXAA K 


36 

37 

29 

29 


29 


Haloacetonitriles 









Chloroacetonitrile 

0.1 

0.3 

ND 

ND 

ND 

ND 

0.3 

0.3 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile® 

1 

4 

3 

2 

NR 

NR 

NR 

NR 

Bromochloroacetonitrile® 

0.1 

0.8 

0.6 

0.6 

0.8 

0.2 

1 

2 

Dibromoacetonitrile® 

0.1 

0.3 

ND 

ND 

<0.5 

ND 

0.3 

0.4 

T richloroacetonitrile® 

0.5 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

Bromodichloroacetonitrile 

0.5 

ND 

ND 

ND 



ND 


Dibromochloroacetonitrile 

0.5 

ND 

ND 

ND 



ND 


T ribromoacetonitrile 

0.95 

ND 

ND 

ND 



ND 


Haloketones 









Chloropropanone 

0.1 

0.3 

0.4 

0.4 

0.4 

0.4 

0.4 

0.2 

1,1 -Dichloropropanone® 

0.1 

2 

1 

0.7 

0.5 

0.8 

0.6 

0.5 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T richloropropanone® 

0.5 

4 

3 

3 

3 

NR 

3 

NR 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

1.0 

<1 

<1 

<1 

1 

NR 

ND 

NR 

1,1,1 -T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-T ribromopropanone 

0.1 

0.3 

0.2 

ND 

ND 

ND 

0.1 

0.1 

1,1,3,3-Tetrachloropropanone 

0.10 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-Tetrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrabromopropanone 

N/A 

NR 

NR 

NR 

NR 

NR 

NR 

NR 


239 









































































Table 17 (continued) 


01/28/2002 

MRL 3 

mq/l 

Plant 4 C 

Compound 

GAC Inf 

GAC Eff 

Plant Eff 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloacetaldehvdes 









Dichloroacetaldehyde 

0.98 

2 

3 

1 

1 

1 

1 

1 

Bromochloroacetaldehyde 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloral hydrate 6 

0.1 

9 

5 

2 

2 

3 

10 

17 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 









Chloronitromethane 

N/A 

ND 

ND 

ND 

ND 


ND 


Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

0.1 

0.2 

0.2 

0.2 

0.2 

0.2 

0.2 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 6 

0.1 

0.6 

0.4 

ND 

ND 

ND 

0.7 

1 

Bromodichloronitromethane 

0.5 

0.6 

0.6 

0.5 



0.7 


Dibromochloronitromethane 

0.5 

ND 

ND 

ND 



ND 


Bromopicrin 

0.5 

ND 

ND 

ND 



ND 


Miscellaneous Compounds 









Methyl ethyl ketone 

0.5 

ND 

ND 

ND 

ND 


ND 


Methyl tertiary butyl ether 

0.2 

0.6 

0.7 

0.6 

0.7 


0.7 


1,1,2,2-Tetrabromo-2-chloroethane 

2.5 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

Benzyl chloride 

0.25 

ND 

ND 

ND 

ND 

NR 

ND 

NR 


240 





































Figure 4 


Seasonal Variability in Trihalomethane Formation at Plants 3 and 4 


■ 11/13/2000 H 2/5/2001 □ 8/1/2001 [110/16/2001 □ 1/28/2002 



Halomethanes. Figure 4 shows the seasonal variability in THM formation at plants 3 and 
4. The sum of the four regulated THMs (THM4) ranged from 31 to 83 pg/L in the plant 4 
effluent. The highest formation was in October 2001 when the bromide level was the highest. 
Note, during most sampling events, plant 4 effluent represented a blend of plant 4 and plant 3 
waters. For example, in August 2001, the plant 4 effluent had 31 pg/L THM4. Based on a plant 
4 flow of 11 mgd—with 37 pg/L THM4 in the GAC effluent—and the addition of 4.2 mgd of 
plant 3 GAC effluent—with 20 pg/L THM4-the theoretical THM4 for the plant 4 effluent was 32 
pg/L. Because the plant 4 distribution system had a free chlorine residual, THM formation 
increased to 38-39 pg/L. 

THM4 ranged from 25 to 55 pg/L in the plant 3 effluent. Pre-chloramination at plant 3 
was more effective at minimizing THM formation in November 2000 than in October 2001, 
most likely due to the difference in bromide concentrations between these two periods (0.06 
versus 0.2 mg/L, respectively). Pre-chloramination was not required in February 2001, as the 
water temperature (7-10°C) and bromide (0.02 mg/L) were relatively low during this time period. 
Thus, pre-chloramination was used at plant 3 at the times of the year in which THM formation 
would be too high with pre-chlorination (e.g., summer and fall). 

Figure 5 shows the impact of bromide on THM speciation in plant 3 effluent. In October 
2001, when the bromide level was the highest, there was the greatest shift in speciation to 
brominated THMs. In February 2001 and January 2002, when the bromide concentration was 
the lowest, chloroform was the major THM species formed. 


241 









































In terms of iodinated THMs, dichloroiodomethane was typically detected in some of the 
samples each quarter. When detected, the concentration of this iodinated THM ranged from 0.25 
to 2 pg/L. In November 2000, bromodiiodomethane and iodoform were also detected in selected 
samples. Dichloroiodomethane and/or bromochloroiodomethane were also found using 
broadscreen-gas chromatography/mass spectrometry (GC/MS) methods (carried out by the 
USEPA) in finished water from plant 3 and plant 4. 

Figure 5 

Impact of Bromide on Trihalomethane Speciation 
in Plant 3 Effluent 



1 / 28/2002 
10 / 16/2001 
8 / 1/2001 
2 / 5/2001 
11 / 13/2000 


Date 

Bromide 

(mg/L) 

01/28/2002 

0.023 

10/16/2001 

0.2 

08/01/2001 

0.05 

02/05/2001 

0.022 

11/13/2000 

0.058 


Halo acids. Figure 6 shows the seasonal variability in haloacetic acid (HAA) occurrence 
at plants 3 and 4. The sum of the five regulated HAAs (HAA5) ranged from 39 to 66 pg/L in the 
plant 4 effluent. The sum of all nine species (HAA9) ranged from 49 to 89 pg/L. The plant 4 
effluent typically represented a blend of plant 4 and plant 3 waters. For example, in August 
2001, the plant 4 effluent had 61 pg/L HAA5 and 74 pg/L HAA9. Based on a plant 4 flow of 11 
mgd before the addition of 4.2 mgd of plant 3 GAC effluent, the theoretical HAA5 and HAA9 
for the plant 4 effluent was 65 and 76 pg/L, respectively. HAA5 and HAA9 were 8.4-32 and 17- 
35 pg/L, respectively, in the plant 3 effluent. The highest HAA occurrence in the plant 3 
effluents was during the winter. 


242 
























Figure 6 


Seasonal Variability in Haloacetic Acid Occurrence at Plants 3 and 4 


■ 11/13/2000 m 2/5/2001 [18/ 1/2001 □ 10/16/200 1 □ 1/28/200 2 



5 


x 


Plant 3 Effluent 


Plant 4 Effluent 



At plant 3, the concentration of HAA9 in the GAC influent was 36-61 pg/L, whereas the 
level in the GAC effluent ranged from not detected (ND) to 21 pg/L. Figure 7 shows that when 
the water temperature was warmer, HAAs were effectively removed, whereas when the water 
was colder, the removal of dihalogenated HAAs (DXAAs) was somewhat diminished and the 
removal of trihalogenated HAAs (TXAAs) was significantly impacted. GAC can provide a 
medium for biological activity, which can result in the control of HAAs. Other research has 
demonstrated that HAAs can be removed by GAC filtration, presumably by biodegradation 
processes within the filter bed (Singer et al., 1999). In another study, DXAAs were found to be 
much better biodegraded than TXAAs in a distribution system with no 
disinfectant residual, and the removal effectiveness was significantly impacted by water 
temperature (Baribeau et al., 2000). 

In contrast, HAAs were typically not removed during GAC filtration at plant 4 (Figure 8), 
and when they were the percentage removed was much less than at plant 3. At plant 3, GAC was 
used in a post-filtration contactor, whereas at plant 4 GAC was used as a filter media in wood tub 
filters. In addition, there was little to no disinfectant residual in the plant 3 GAC effluents, 
whereas there was a free chlorine residual in the plant 4 GAC effluents. The operational use of 
GAC was different at the two plants. 


243 






















































HAA Removal 


Figure 7 


Impact of Temperature on Removal 
of Haloacetic Acids on Plant 3 GAC Filter 


□ DXAA Removal DTXAA Removal ■ Temperature 



11/13/2000 2/5/2001 8/1/2001 10/16/2001 1/28/2002 


Figure 8 


Impact of Temperature on Removal 
of Haloacetic Acids on Plant 4 GAC Filter 


D DXAA Removal DTXAA Removal * Temperature 



244 


Temperature (C) 






















































Figure 9 shows how HAAs were reformed during post-GAC chlorination, whereas 
THMs—which were not removed during GAC filtration—increased in formation through the 
treatment process. The levels of HAAs formed during post-GAC chlorination were less than 
what was initially formed by pre-chlor(am)ination. Because the HAAs were effectively removed 
by GAC during the warmer months, HAA occurrence in the plant effluent was primarily from 
the post-GAC chlorination. Alternatively, during the colder months, HAAs in the plant effluent 
were from a combination of HAAs not removed by GAC and that formed during post-GAC 
chlorination. Thus, HAA occurrence in the plant effluent was higher in the winter at plant 3. 


Figure 9 


Formation and Removal of Trihalomethanes 
and Haloacetic Acids at Plant 3 




THM4 DXAA TXAA 

◄-02/05/2001 -► 


THM4 DXAA TXAA 

◄-10/16/2001 -► 


245 












































































































Figure 10 shows the impact of bromide on HAA speciation in the plant 3 GAC influent. 
In October 2001, when the bromide level was the highest, there was the greatest shift in 
speciation to brominated HAAs. In February 2001 and January 2002, when the bromide 
concentration was the lowest, dichloro- and trichloroacetic acid were the major HAA species 
formed. 


Figure 10 


Impact of Bromide on Haloacetic Acid Speciation 
in Plant 3 GAC Influent 



Date 

Bromide 

(mg/L) 

01/28/2002 

0.023 

10/16/2001 

0.2 

08/01/2001 

0.05 

02/05/2001 

0.022 

11/13/2000 

0.058 


* ? # 


1/28/2002 
10/16/2001 
T 8/1/2001 
/ 2/5/2001 
11/13/2000 




& op°' 


<D N ip _ 


Figure 11 shows the impact of disinfection scenario on HAA speciation in plants 3 and 4 
GAC influent samples. At plant 4, pre-chlorination resulted in the formation of more TXAAs 
than DXAAs. Likewise, Cowman and Singer (1996) found that the TXAAs were the dominant 
HAA species in their study during chlorination. At plant 3, during pre-chloramination, DXAAs 
were formed to a higher extent than the TXAAs. Krasner and co-workers (1996) found that 
chloramines minimized the formation of THMs and TXAAs better than that of DXAAs. 
Likewise, Cowman and Singer (1996) found that DXAAs were the principal HAA species 
formed from chloramination. 

February 2001 results from UNC also show the presence of another target halo-acid, 3,3- 
dichloropropenoic acid, at levels of 1.5 and 0.9 pg/L, respectively, in finished waters from plant 
3 and plant 4 (Table 18). 3,3-Dichloropropenoic acid, as well as trichloropropenoic acid, was 
also identified in broadscreen GC/MS analyses carried out by the USEPA. 


246 










































Figure 11 


Impact of Disinfection Scenario on HAA Speciation 
in Plant 3 and 4 GAC Influent Samples 


Plant 3 DXAAs mm Plant 3 TXAAs - - A- • Plant 4 DXAAs Plant 4 TXAAs 



Haloacetonitriles. In other research, haloacetonitriles (HANs) have been found to be 
produced at approximately one-tenth the level of the THMs (on a weight basis) (Krasner et al., 
1989). In the latter study, the 25th and 75th percentile ratios of HANs to THMs were 0.065 and 
0.147, respectively. The HAN to THM relationship had originally been established between 
dichloroacetonitrile (DCAN) and chloroform (trichloromethane [TCM]) (Oliver, 1983). 

Figure 12 shows that DCAN formation in GAC influent samples at plants 3 and 4 was 
equal to or higher than one-tenth the level of chloroform. A linear regression of the data, except 
for the August 2001 data that were atypical, indicated that DCAN was ~17 % of the level of 
chloroform. This value was somewhat higher than the 75th percentile ratio observed by Krasner 
and colleagues (1989). 

In these samples, the pH ranged from 5.5 to 6.2. In other research, THM formation has 
been shown to be lower at acidic pH and DCAN formation has been higher at acidic pH, whereas 
dichloroacetic acid (DCAA) formation was found to be relatively insensitive to pH (Stevens et 
al., 1989). Figure 13 shows the relationship between DCAN and DCAA formation for these 
samples. A linear regression of the data, including the August 2001 samples, indicated that 
DCAN was ~18 % of the level of DCAA. These results suggest that the pH of chlorination 
within plants 3 and 4 was, in part, impacting the relative formation of DCAN, chloroform, and 
DCAA. 


247 




























Figure 12 


Dichloroacetonitrile (DCAN) Formation as a Function of Chloroform 
(TCM) Formation in Plants 3 and 4 GAC Influent Samples 



Figure 13 


Dichloroacetontrile (DCAN) Formation as a Function of Dichloroacetic 
Acid (DCAA) Formation in Plants 3 and 4 GAC Influent Samples 



248 





DCAN was 0.9-4 and 0.1-1.6 pg/L in the plant 3 GAC influent and effluent, respectively. 
Figure 14 shows that the concentration of DCAN was significantly reduced in passing through 
the GAC when the water temperature was warm. DCAN was 2.6-10 and 2.8-10 pg/L in the 
plant 4 GAC influent and effluent, respectively. The level of DCAN was generally unchanged in 
passing through the plant 4 GAC filters (Figure 14). Likewise, the brominated analogues of 
DCAN were reduced in concentration in passing through the plant 3 GAC filter when the water 
temperature was warm, whereas the plant 4 GAC filters had no significant impact. Similar to the 
HAAs, the plant 3 GAC filter resulted in a significant reduction in the concentration of the 
FIANs, and the phenomenon was temperature sensitive, whereas the plant 4 GAC filter did not 
significantly reduce the concentration of the HANs. 

Figure 15 shows the impact of bromide on HAN speciation in plant 3 GAC influent. In 
October 2001, when the bromide level was the highest, there was the greatest shift in speciation 
to brominated HANs. In February 2001 and January 2002, when the bromide concentration was 
the lowest, DCAN was the major HAN species formed. 

The plant 4 effluent typically represented a blend of plant 4 and plant 3 waters. For 
example, in August 2001, the plant 4 effluent had 6 pg/L DCAN. Based on a plant 4 flow of 11 
mgd before the addition of 4.2 mgd of plant 3 GAC effluent, the theoretical DCAN concentration 
for the plant 4 effluent was 7 pg/L. 

Finally, sub-pg/L levels of one of the EPA study HANs (i.e., chloroacetonitrile) were 
detected in selected samples. Broadscreen GC/MS analyses also revealed the presence of 
tribromoacetonitrile in one sample (finished water from plant 3, November 2000). 

Haloketones. Figure 16 shows the impact of bromide on haloketone (HK) speciation in 
plants 3 and 4 GAC influent samples. Specifically, the two HK species in the Information 
Collection Rule (ICR) (1,1-dichloro- and 1,1,1-trichloropropanone) were evaluated along with 
two brominated analogues included in the EPA DBP study (1,1-dibromo- and l-bromo-1,1- 
dichloropropanone). In October 2001, when the bromide level was the highest, there was an 
increase in the formation of both of these brominated HKs when compared to the August 2001 
sampling, which was accompanied by decreases in the concentrations of the corresponding 
chlorinated species. 

In addition to the formation of selected brominated species, other EPA study HKs (e.g., 
chloro-, 1,1,3-trichloro-, 1,1,3,3-tetrachloro-, and 1,1,1,3-tetrachloropropanone) were detected in 
selected samples. Furthermore, pentachloropropanone and hexachloropropanone were detected 
at plants 3 and 4 in November 2000, August 2001, and January 2002 by the USEPA using 
broadscreen-GC/MS methods. 


249 


DCAN Removal 


Figure 14 


Impact of Temperature on Removal 
of Dichloroacetonitrile on GAC Filters 

□ Plant 3 DCAN Removal □ Plant 4 DCAN Removal ■Temperature 



Figure 15 


Impact of Bromide on Haloacetonitrile Speciation 
in Plant 3 GAC Influent 



Date 

Bromide 

(mg/L) 

01/28/2002 

0.023 

10/16/2001 

0.2 

08/01/2001 

0.05 

02/05/2001 

0.022 

11/13/2000 

0.058 




1/28/2002 
10/16/2001 
/ 8/1/2001 
A 2/5/2001 
11/13/2000 


////// 






<y \0 

<P° OP 

O' V \V> 


250 

















































Figure 16. Impact of bromide on haloketone speciation in plants 3 and 4 GAC influent 
samples: bromide = 0.05 and 0.2 mg/L on 8/1/01 and 10/16/01, respectively. 




Plant 4, 10/16/01 
Plant 4, 8/1/01 
Plant 3, 10/16/01 
Plant 3, 8/1/01 


Plant 4, 10/16/01 
Plant 4, 8/1/01 
Plant 3, 10/16/01 
Plant 3, 8/1/01 


Figure 17 shows that the concentrations of 1,1-dichloro- and 1,1,1-trichloropropanone 
were significantly reduced in passing through the GAC when the water temperature was warm. 
The levels of these two HKs were generally unchanged in passing through the plant 4 GAC 
filters (Figure 18). Likewise, many of the EPA DBP study HKs were reduced in concentration in 
passing through the plant 3 GAC filter when the water temperature was warm, whereas the plant 
4 GAC filters had no significant impact. Similar to the HAAs, the plant 3 GAC filter resulted in 
a significant reduction in the concentration of many of the HKs, and the phenomenon was 
temperature sensitive, whereas the plant 4 GAC filter did not significantly reduce the 
concentration of the HKs. 

Figure 19 shows how most HKs that were reduced in concentration in the plant 3 GAC 
filter were reformed during post-GAC chlorination, whereas chloropropanone—which was not 
removed during GAC filtration—increased somewhat in concentration through the treatment 
process. The levels of HKs formed during post-GAC chlorination were less than what was 
initially formed by pre-chlor(am)ination. 


251 





















Haloketone Removal 


Figure 17 


Impact of Temperature on Removal 
of Haloketones on Plant 3 GAC Filter 


□ 1,1-Dichloropropanone Removal □ 1,1,1 -Trichloropropanone Removal B Temperature 


re 

> 

o 

E 
o> 
a.: 
a> 

c 

o 

*-» 

a> 

o 

re 

X 




30 

25 


20 


Temperature 
not available 


15 



10 

- 5 

- 0 


11/13/2000 2/5/2001 8/1/2001 10/16/2001 1/28/2002 


Figure 18 

Impact of Temperature on Removal 
of Haloketones on Plant 4 GAC Filter 


01,1-Dichloropropanone Removal 01,1,1-Trichloropropanone Removal ■ Temperature 


50% 


40% 


30% 


20 % 


10 % - 


0 % 


- 10 % 


11/13/2000 


2/5/ 




T~ 

I 
{ 

I#* 




30 


24 


- 18 _ 
O 

<u 

i_ 

12 re 

0) 

a 

E 

0) 


8 / 1/2001 


10/16/2001 


1/28/2002 

Temperature 


not available 


-6 


252 


Temperature (C) 














































Figure 19 


Formation and Removal of Haloketones 
at Plant 3: 10/16/01 



Haloacetaldehydes. Figure 20 shows the impact of bromide on haloacetaldehyde 
speciation in the plant 3 GAC influent. Note, the results for chloral hydrate in November 2000 
represented the sum of the concentrations of chloral hydrate and bromochloroacetaldehyde, as 
these two DBPs co-eluted with the originally used GC method. In October 2001, when the 
bromide level was the highest, there was a significant formation of bromochloro- and 
tribromoacetaldehyde. In August 2001, there was also a significant formation of these two 
brominated haloacetaldehydes. Although the bromide concentration was lower in August, the 
higher water temperature combined with the bromide probably contributed to the formation of 
these brominated DBPs in that month. In February 2001 and January 2002, when the bromide 
concentration was the lowest, both brominated species were formed at very low levels or were 
not detected. In addition, another brominated aldehyde (2-bromo-2-methylpropanal) was 
detected at plant 3 in November 2000 by the USEPA using broad-screen GC/MS methods. 

Figure 21 shows the impact of disinfection scenario on haloacetaldehyde speciation in 
plants 3 and 4 GAC influent samples. At plant 4, pre-chlorination resulted in the formation of 
more trihalogenated acetaldehydes than dihalogenated acetaldehydes. At plant 3, during pre- 
chloramination, dihalogenated acetaldehydes were typically formed to a higher extent than the 
trihalogenated acetaldehydes. Note, because bromochloroacetaldehyde results in November 
2000 were included in the chloral hydrate (trichloroacetaldehyde) results due to co-elution on the 
GC, the speciation in that month could not be properly resolved. 


253 


























































Haloacetaldehyde (pg/L) 


Figure 20 


Impact of Bromide on Haloacetaldehyde Speciation 
in Plant 3 GAC Influent 


■ 11/ 13/2 000 ^ 2/5/2001 □ 8/1/2001 □ 10/ 16/200 1 □ 1/28/2002 


5.0 


4.0 


3.0 


2.0 


1.0 


0.0 



Dichloroacetaldehyde Bromochloroacetaldehyde 


Chloral hydrate 


T ribromoacetaldehyde 


Bromochloroacetaldehyde and chloral hydrate co-eluted in 11/13/00 sample 

1 _ 


Date 

Bromide 

(mg/L) 

11/13/2000 

0.058 

02/05/2001 

0.022 

08/01/2001 

0.05 

10/16/2001 

0.2 

01/28/2002 

0.023 


Figure 21 

Impact of Disinfection Scenario on Haloacetaldehyde Speciation 
In Plants 3 and 4 GAC Influent Samples 


Plant 3 Dihalogenated Acetaldehydes 


Plant 3 Trihalogenated Acetaldehydes 


■ • -A- • Plant 4 Dihalogenated Acetaldehydes ■ Plant 4 Trihalogenated Acetaldehydes 



11/13/2000 2/5/2001 8/1/2001 10/16/2001 1/28/2002 


254 
































































Young and colleagues (1995) observed that chloral hydrate production was minimized by 
chloramination, whereas the formation of DCAN was similar during chlorination and 
chloramination, and where DCAN was produced from the reaction of chloramines with reaction 
by-products such as dichloroacetaldehyde. The relative formation of di- and trihalogenated 
acetaldehydes with pre-chlorination versus pre-chloramination was similar to that observed for 
DXAAs and TXAAs (Figure 11). 

Figure 22 shows that the concentrations of dichloroacetaldehyde and chloral hydrate were 
significantly reduced in passing through the GAC when the water temperature was warm. The 
levels of these two haloacetaldehydes were generally unchanged in passing through the plant 4 
GAC filters (Figure 23). Likewise, the brominated haloacetaldehydes were reduced in 
concentration in passing through the plant 3 GAC filter when the water temperature was warm, 
whereas the plant 4 GAC filters typically had no significant impact. Similar to the HAAs, the 
plant 3 GAC filter resulted in a significant reduction in the concentration of the 
haloacetaldehydes, and the phenomenon was temperature sensitive, whereas the plant 4 GAC 
filter typically did not significantly reduce the concentration of the haloacetaldehydes. 


Figure 22 

Impact of Temperature on Removal 
of Haloacetaldehydes on Plant 3 GAC Filter 


E3 Dichloroacetaldehyde Removal □ Chloral Hydrate Removal * Temperature 

100 % 


_ 80% 

re 

> 

o 

E 

0) 

O 60% 

T3 

>v 

.C 

0 ) 

2 

2 40% 

o 

o 

re 

o 

re 

X 20% 


0 % 

11/13/2000 2/5/2001 8/1/2001 10/16/2001 1/28/2002 



255 


























Figure 23 


Impact of Temperature on Removal 
of Haloacetaldehydes on Plant 4 GAC Filter 

□ Dichloroacetaldehyde Removal □ Chloral Hydrate Removal M Temperature 



‘Negative value corresponds to sample with more haloacetaldehyde in filter effluent than in filter influent 


Figure 24 shows how some of the haloacetaldehydes were reformed during post-GAC 
chlorination at plant 3. The levels of haloacetaldehydes formed during post-GAC chlorination 
were less than what was initially formed by pre-chlor(am)ination. 

Broadscreen analyses carried out at the USEPA also revealed the presence of four 
haloaldehydes that were not among the targeted list (Table 21). These are tentatively identified 
as 2-bromo-2-methylpropanal, iodobutanal, dichloropropenal, and 4-chloro-2-butenal. The 
identification of iodobutanal represents the first time that an iodinated aldehyde has been 
identified as a DBP. This compound was not present in the mass spectral library databases, but 
high resolution electron ionization (El) mass spectrometry confirmed the empirical formula 
assignment of C 4 H 7 OI (molecular weight of 198). An exact isomer assignment for this molecule 
was not possible from the MS data obtained. 


256 




































Figure 24 


Formation and Removal of Haloacetaldehydes 
at Plant 3: 10/16/01 


■ Rapid Mix UGAC Influent DGAC Effluent 11 Plant Effluent 


4.5 

4 


3.5 


U) 


o 

•a 

>s 

JZ 

Q> 

2 

re 

+* 

v 

o 

re 

o 

re 

X 


2.5 


1.5 


0.5 

0 



Dichloroacetaldehyde Bromochloroacetaldehyde Chloral hydrate Tribromoacetaldehyde 


Halonitromethanes. Sub-pg/L levels of chloropicrin (trichloronitromethane) were 
detected in selected samples. Dichloronitromethane was detected in selected samples in October 
2001 and in January 2002. Brominated analogues of chloropicrin were detected in the plant 3 
GAC influent in October 2001 when the bromide concentration was the highest (Figure 25). 
Because the occurrence of these DBPs were typically at or near their minimum reporting levels 
(MRLs), it was not possible to study their fate through the GAC filters on most sample dates. 
However, the data from February 2001 (Figure 26) suggest that chloropicrin was removed during 
GAC filtration at plant 3, not plant 4, even though the water temperature was relatively cold. 
Dichloronitromethane was also detected in finished water in August 2001 using broadscreen 
GC/MS techniques. 
























































Figure 25 


Impact of Bromide on Halonitromethane Speciation in Plant 3 GAC Influent: 
Bromide = 0.02 and 0.2 mg/L on 1/28/02 and 10/16/01, Respectively 


"S) 

0.5- 

2. 

0) 

c 

0.4- 

re 

.c 

■4-* 

CD 

0.3 

E 

o 

i_ 

44 

0.2 

‘E 

o 

0.1 

re 

X 

0 



/yv ✓ . 


0 <P Q<^ r x>' 


10 / 16/2001 

1 / 28/2002 


* 4? 




<& 


4? <? 


& <o N ' 


o^° ^° N 


<y 

rv» 




<*> N 


4T 






Figure 26 


Formation and Removal of Chloropicrin 
at Plants 3 and 4: 2/5/01 


NS = Not Sampled 



Rapid Mix 

GAC 


Plant 4 


Influent 


Plant 3 


GAC Effluent 


Plant Effluent 


258 


















































Volatile Organic Compounds (VOCs). Carbon tetrachloride, which is a VOC and a 
possible DBP, was detected (0.3-0.8 pg/L) at both plants in November 2000, but was not found 
in the raw water (MRL = 0.06 pg/L). As mentioned in a previous chapter, carbon tetrachloride 
has been detected by some utilities in gaseous chlorine cylinders (EE&T, 2000), due to 
imperfections in the manufacturing process or improper cleaning procedures. 

Methyl tertiary butyl ether (MtBE) was detected in the raw water on all of the sample 
dates, with concentrations of 0.4 to 1 pg/L (Figure 27). The level of MtBE was unchanged 
through either treatment plant. GAC at plant 3 did not remove MtBE. MtBE is a VOC (e.g., a 
gasoline additive), not a DBP, but is of concern due to widespread contamination of source 
waters. 


Figure 27 


Occurrence of Methyl tertiary Butyl Ether (MtBE) 
in Raw Water and in Plant 3 and 4 Effluents 



Methyl ethyl ketone (MEK) was detected in the raw water on August 1, 2001 at a 
concentration of 28 pg/L (Figure 28). The level of MEK decreased through both treatment 
plants. MEK is an industrial solvent. The tremendous amount of rainfall the weekend before the 
sampling may have contributed to the presence of this solvent in the raw water (e.g., due to 
runoff). MEK was detected in the raw water on October 16, 2001 at 0.6 pg/L. After pre- 
chlor(am)ination, the level of MEK was 3 pg/L. MEK is also a DBP (an oxidation by-product). 
MEK was removed on the plant 3 GAC in October 2001, but only a small percentage of it was 
removed on the plant 4 GAC. MEK is a carbonyl, and various carbonyls have been shown to be 
biodegradable on biologically active filters (Krasner et al., 1993). 


259 



































Figure 28 


Occurrence of Methyl Ethyl Ketone (MEK) 
in Raw Water and in Plant 3 and 4 Effluents 


■ Raw Water il GAC Influent □ GAC Effluent □ Plant Effluent 



HalogenatedFuranones. Table 20 presents data for 3-chloro-4-(dichloromethyl)-5- 
hydroxy-2[5H]-furanone, otherwise known as MX; (E)-2-chloro-3-(dichloromethyl)-4- 
oxobutenoic acid, otherwise known as EMX; and mucochloric acid (MCA), which can be found 
as a closed ring or in an open form. In October 2001, MX was detected at 0.18 pg/L (180 ng/L) 
in the finished water of plant 3 (which used chlorine-chloramine disinfection), which was higher 
than levels reported in a survey of Australian waters (<90 ng/L) (Simpson and Hayes, 1998). 
However, water quality and treatment/disinfection schemes may be different in Australia than in 
the United States. In particular, regulatory requirements in Australia are significantly different 
than in the United States. Subsequently, MX levels dropped in the distribution system to 0.013 
pg/L (13 ng/L). EMX levels were 0.10 pg/L in the finished water, but dropped to 0.03 pg/L in 
the distribution system. Mucochloric acid {ring form) was 0.53 pg/L in the GAC influent and 
0.05 pg/L in the GAC effluent. Likewise, the open form of mucochloric acid was 0.11 and 0.014 
pg/L in the GAC influent and effluent, respectively. Similar to that of many other DBPs in this 
study, MCA {ring and open forms) was removed on the biologically-active GAC filters. MCA 
{ring form) was partially re-formed at 0.13 pg/L in the finished water, and its concentration 
remained steady at 0.12 pg/L in the distribution system. The open form of mucochloric acid was 
re-formed in the finished water (0.03 pg/L) and continued to increase in the distribution system 
(0.16 pg/L). The concentrations of MCA ring and open forms were qualitative, due to sample 
matrix co-elutants on the GC column. Due to the relatively high level of bromide in the source 
water (0.2 mg/L), brominated MX analogs (BMXs) would be expected; however, they were not 
analyzed for in these samples. 


260 

























































Plant 4, which used chlorine disinfection (applied both to the raw and filtered waters), 
showed much lower levels of MX (0.015 pg/L) in the finished water, but higher levels (0.02 
pg/L) in the chlorinated distribution system. Only a small amount of EMX was detected in 
finished water from plant 4 (0.011 pg/L), which decreased to below detection in the distribution 
system. Mucochloric acid levels (both ring and open forms) were higher in the finished water 
from plant 4 (0.71 and 0.19 pg/L) than in plant 3 (0.13 and 0.03 pg/L), which contributed to total 
levels of MX analogs being higher in plant 4 (Figure 29). At plant 4, spent GAC filters were not 
effective in removing the MX analogues initially formed. This is similar to what was observed 
for many other DBPs in this study. 

Other Halogenated DBPs. A few additional halogenated DBPs were also detected. UNC 
methods detected dichloroacetamide at 1.2 pg/L in finished water from plant 3 in February 2001 
(Table 18). Dichloroacetamide was also observed in the distribution system (2.1 pg/L, plant 3) 
in October 2001 (Table 19). In addition, broadscreen GC/MS analyses revealed the presence of 
trichlorophenol and trichlorobenzene-1,2-diol (Table 21) in plant 3 water pre-treated with 
chlorine (January 2002). These halo-phenols were not observed in the corresponding raw, 
untreated water, and were not detected in the plant effluent. 

Non-Halogenated DBPs. Targeted non-halogenated DBPs observed included trans-2- 
hexenal (plant 4, February 2001) (Table 18) and dimethylglyoxal (plant 4, October 2001) (Table 
19). Levels were 0.7 and 1.4 pg/L, respectively. Several carboxylic acids were also identified 
as DBPs using broadscreen GC/MS analysis (Table 21). Many carboxylic acids are also seen in 
the raw, untreated water. However, many were also judged to be formed as DBPs, as their levels 
increased substantially (2-3X) in the treated waters versus the raw, untreated waters. 


261 


Table 18. Additional target DBP results Qng/L) at plants 3 and 4 (2/5/01) 


2/5/01 

Pla 

Cl 2 /1 

int 3 a 

MH 2 C1 

Plant 4 

Cl 2 

Compound 

Raw 

FI 

FE 

PE 

DS 

SDS 

FI 

FE 

PE 

DS 

SDS 

Monochloroacetaldehyde 

0 

0.4 

0.3 

0.4 

0.3 

0.3 

1.9 

2.2 

0.5 

0.5 

0.4 

Dichloroacetaldehyde 

0 

4.7 

2.9 

4.3 

3.8 

3.7 

3.9 

3.8 

3.5 

3.6 

3.6 

Bromochloroacetaldehyde 

0 

0.5 

0.5 

0.7 

0.3 

0.5 

0.9 

0.6 

0.8 

0.6 

0.5 

3,3-Dichloropropenoic acid 

0 

0.7 

0.5 

1.5 

0.4 

1.6 

1.0 

0.6 

0.9 

0.9 

1.2 

Bromochloromethylacetate 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

Dichloroacetamide 

0 

0 

0 

1.2 

1.0 

1.9 

0 

0 

0.5 

0.4 

0.6 

TOX (pg/L as Cl ) 

0.6 

105.1 

47.4 

87.3 

88.0 

110.1 

127.6 

31.8 

188.3 

154.9 

138.5 

Cyanoformaldehyde 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

5-Keto-l-hexanal 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

6-Hydro xy-2-hexanone 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

Dimethylglyoxal 

< 0.4 

< 0.4 

< 0.4 

< 0.4 

< 0.4 

< 0.4 

< 0.4 

< 0.4 

< 0.4 

< 0.4 

< 0.4 

?ra«s-2-Hexenal 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

0.7 

0.7 

0.6 


treatment plant sampled at (1) raw water, (2) GAC filter influent (FI), (3) GAC filter effluent 
(FE), (4) finished water at plant effluent (PE), (5) distribution system (DS) at average detention 
time, and (6) simulated distribution system (SDS) at maximum detection time. 


Table 19. Additional target DBP results (pg/L) at plants 3 and 4 (10/16/01) 


10/16/01 

Pla 

Cl 2 /1 

int 3* 

VH 2 C1 

Plant 4 

Cl 2 

Compound 

Raw 

FI 

FE 

PE 

DS 

SDS 

FI 

FE 

PE 

DS 

SDS 

Monochloroacetaldehyde 

0 

1.2 

0 

0 

0.5 

0.6 

1.9 

0.4 

0.4 

0.5 

0.6 

Dichloroacetaldehyde 

0 

5.1 

0.5 

0.5 

1.2 

1.6 

5.4 

4.2 

4.4 

4.8 

6.1 

Bromochloroacetaldehyde 

0 

3.1 

0 

0 

0.9 

1.5 

1.1 

1.5 

1.8 

2.0 

2.8 

3,3-Dichloropropenoic acid 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

Bromochloromethylacetate 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

Dichloroacetamide 

0 

1.8 

0.2 

0 

2.1 

4.8 

0 

0 

0 

0 

0 

TOX (pg/L as Cl ) 

29.1 

216.0 

82.3 

161.0 

162.0 

141.0 

291.0 

278.0 

278.0 

257.0 

323.0 

Cyanoformaldehyde 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

5-Keto-l-hexanal 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

6-Hydroxy-2-hexanone 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

Dimethylglyoxal 

< 0.4 

< 0.4 

< 0.4 

< 0.4 

< 0.4 

< 0.4 

< 0.4 

< 0.4 

1.4 

1.6 

2.4 

trans - 2-Hexenal 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 

< 0.1 


treatment plant sampled at (1) raw water, (2) GAC filter influent (FI), (3) GAC filter effluent 
(FE), (4) finished water at plant effluent (PE), (5) distribution system (DS) at average detention 
time, and (6) simulated distribution system (SDS) at maximum detection time. 


262 
























































Table 20. Halogenated furanone results (ng/L) at plants 3 and 4 (10/16/01) 


10/16/01 

I 

Cl 

5 lant 3° 

2 /NH 2 Cl 

Plant 4 

Cl 2 

Compound 

Raw 

FI 

FE 

PE 

DS 

FI 

FE 

PE 

DS 

MX 

< 0.02 

0.03 

< 0.02 

0.18 

< 0.02 

( 0 . 013 ) 

0.05 

< 0.02 

< 0.02 

( 0 . 015 ) 

0.02 

EMX 

< 0.02 

< 0.02 

0.05 

0.10 

0.03 

< 0.02 

0.02 

< 0.02 

( 0 . 011 ) 

< 0.02 

Mucochloric acid (ring) 

< 0.02 

0.53 

0.05 

0.13 

0.12 

0.86 

1.00 

0.71 

0.47 

Mucochloric acid (open) 

< 0.02 

0.11 

< 0.02 

( 0 . 014 ) 

0.03 

0.16 

0.25 

0.13 

0.19 

0.14 


treatment plant sampled at (1) raw water, (2) GAC filter influent (FI), (3) GAC filter effluent 
(FE), (4) finished water at plant effluent (PE), and (5) distribution system (DS) at average 
detention time. Value in parenthesis is less than the MRJL. 


Figure 29. Halogenated furanones. 


Plants 3 and 4 (10/16/01) 


1.20 


1.00 


C _l 

c 1 
ra >3 

3 w 

u. c 
■o -2 

£ 2 
m i: 
c c 
0) © 
U> o 
o c 

re .9 


0.80 


0.60 


0.40 


0.20 


0.00 


Raw 


I MX M EMX □ MCA (ring) 3 MCA (open) 


FI 

CI2+NH3 


UJ 


FE 
GAC 
Plant 3 


PE DS/ave 
CI2+NH3 


Sampling Sites 



263 
































































































Table 21. Occurrence of other DBPs a at plants 3 and 4 



11/13/00 

8/1/01 

1/28/02 

Compound 

Plant 3 

Plant 3 

Plant 4 

Plant 3 

Plant 3 


C1 2 /NH 2 C1 

C1 2 /NH 2 C1 

Cl 2 

Pre- Cl 2 

C1 2 /NH 2 C1 

Halomethanes 






Bromodichloromethane 

X 

- 

X 

X 

X 

Dibromochloromethane 

X 

X 

X 

X 

X 

Bromoform 

X 

X 

X 

X 

X 

Dichloroiodomethane 

X 

X 

X 

- 

- 

Bromochloroiodomethane 

X 

- 

- 

X 

- 

Haloacids 






Dichloroacetic acid 

X 

X 

X 

- 

- 

Bromochloroacetic acid 

X 

- 

X 

- 

- 

Dibromoacetic acid 

X 

X 

- 

- 

- 

Trichloroacetic acid 

X 

X 

X 

X 

X 

3,3-Dichloropropenoic ac {d 

- 

X 

X 

- 

- 

Trichloropropenoic acid 

- 

X 

X 

- 

X 

Haloacetonitriles 






Dichloroacetonitrile 

X 

X 

X 

X 

- 

Bromochloroacetonitrile 

X 

X 

X 

X 

X 

Dibromoacetonitrile 

X 

X 

X 

X 

- 

Tribromoacetonitrile 

X 

- 

- 

- 

- 

Haloaldehvdes 






Dichloroacetaldehyde 

X 

X 

X 

X 

X 

T richloroacetaldehyde 

- 

X 

X 

- 

- 

2-Bromo-2-methylpropanal 

X 

X 

X 

X 

X 

Iodobutanal c 

X 

- 

- 

- 

- 

Dichloropropenal c 

- 

X 

X 

- 

- 

4-Chloro-2-butenal 

- 

- 

- 

X 

X 

Haloketones 






1,1 -Dichloropropanone 

X 

- 

X 

X 

X 

1,1,1 -T richloropropanone 

X 

X 

X 

X 

X 

1 -Bromo-1,1 -dichloropropanone 

X 

- 

X 

- 

- 

1,1,3,3-Tetrachloropropanone 

X 

X 

X 

X 

X 

Pentachloropropanone 

X 

X 

X 

X 

X 

Hexachloropropanone 

X 

- 

X 

X 

- 

Halonitromethanes 






Dichloronitromethane 

- 

X 

X 

- 

- 

Miscellaneous Haloeenated DBPs 






Trichlorophenol 

- 

- 

- 

X 

- 

Trichlorobenzene-1,2-diol 

- 

- 

- 

X 

- 


264 























Table 21 (continued) 



11/13/00 

8/1/01 

1/28/02 

Compound 

Plant 3 

Plant 3 

Plant 4 

Plant 3 

Plant 3 


C1 2 /NH 2 C1 

C1 2 /NH 2 C1 

Cl 2 

Pre- Cl 2 

C1 2 /NH 2 C1 

Non-haloeenated DBPs 






3-Methylbutanoic acid 

- 

- 

X 

- 

- 

Pentanoic acid 

x 

- 

- 

- 

- 

Hexanoic acid 

X 

- 

- 

- 

- 

Heptanoic acid 

x 

- 

- 

- 

- 

Octanoic acid 

X 

- 

- 

- 

X 

Nonanoic acid 

- 

- 

- 

- 

X 

Decanoic acid 

- 

- 

- 

- 

X 

Dodecanoic acid 

- 

- 

X 

- 

X 

Tetradecanoic acid 

- 

- 

- 

- 

X 

Pentadecanoic acid 

- 

- 

- 

- 

X 

Hexadecanoic acid 

X 

- 

- 

- 

X 

Octadecanoic acid 

- 

X 

- 

- 

- 

Butanedioic acid 

- 

- 

- 

- 

X 

Pentanedioic acid 

- 

- 

- 

- 

X 

Hexanedioic acid 

- 

- 

- 

- 

X 

Octanedioic acid 

- 

- 

- 

- 

X 

Decanedioic acid 

- 

- 

- 

- 

X 

Undecanedioic acid 

- 

- 

- 

- 

X 


a DBPs detected by broadscreen gas chromatography/mass spectrometry (GC/MS) technique. 
b Compounds listed in italics were confirmed through the analysis of authentic standards; 
haloacids and non-halogenated carboxylic acids identified as their methyl esters. 
c Exact isomer not known. 

SDS Testing. Because plant 3 used chloramines, most DBPs were found to be relatively 
stable in concentration in the distribution system and in SDS testing. Because plant 4 used free 
chlorine, THMs and some of the other DBPs were found to increase in concentration in the 
distribution system and in SDS testing. Figure 30 shows that there was an increase in THM 
formation—especially for the bromochloro species—during the maximum detention time 
(140-hr) SDS test of the plant 3 effluent in October 2001 when the bromide level was the 
highest. However, the formation of the THMs increased by a much higher amount during SDS 
testing of the plant 4 effluent. 

Figure 31 shows the formation and stability of the HANs in SDS testing in October 2001. 
Although DCAN can undergo base-catalyzed hydrolysis (Stevens et al., 1989), DCAN was 
stable (and continued to form) in SDS testing at plants 3 and 4, as the pH was 7.0-7.4. The other 
HANs, including chloroacetonitrile (an EPA study DBP), were stable during this SDS testing. 

Figure 32 shows the formation and stability of the haloketones in SDS testing in October 
2001. Stevens and colleagues (1989) found 1,1,1-trichloropropanone to be more sensitive to pH 
than DCAN. In the SDS testing, it did degrade over time. In addition, its brominated analogue 
1-bromo-1,1-dichloropropanone, as well as 1,1,3,3-tetrachloropropanone, were detected in the 
plant effluent samples but not in the SDS testing. Alternatively, chloropropanone was stable 
during this SDS testing. 


265 











HAN (pg/L) THM (pg/L) 


Figure 30 


Formation of Trihalomethanes in Simulated Distribution System (SDS) 
Testing (10/16/01): Chloramine and Chlorine Residuals in Plants 3 and 
4 SDS Tests, Respectively; Average and Maximum Detention Times of 

77 and 140 hr, Respectively 


■ Plant 3 Eff m Plant 3 SDS/Ave 0 Plant 3 SDS/Max 

03 Plant 4 Eff □ Plant 4 SDS/Ave (3 Plant 4 SDS/Max 



Chloroform Bromodichloromethane Dibromochloromethane Bromoform 


Figure 31 


Formation and Stability of Haloacetonitriles in SDS Testing (10/16/01) 


■ Plant 3 Eff m Plant 3 SDS/Ave □ Plant 3 SDS/Max 

■ Plant 4 Eff □ Plant 4 SDS/Ave H Plant 4 SDS/Max 



Chloroacetonitrile Dichloroacetonitrile Bromochloroacetonitrile Dibromoacetonitrile 


NR = Not reported 


266 




















































































































Figure 33 shows the formation and stability of the haloacetaldehydes in SDS testing in 
October 2001. Chloral hydrate can also undergo base catalyzed hydrolysis (Stevens et al., 1989). 
In the SDS testing of the chlorinated water from plant 4, it initially increased in formation and 
then was somewhat degraded at maximum detention time. Many non-THM DBPs are known to 
simultaneously form and degrade in a chlorinated distribution system. Alternatively, dichloro- 
and bromochloroacetaldehyde were stable during this SDS testing. 


Figure 32 

Formation and Stability of Haloketones in SDS Testing (10/16/01) 


■ Plant 3 Eff m Plant 3 SDS/Ave E Plant 3 SDS/Max 

m Plant 4 Eff□ Plant 4 SDS/Ave_B Plant 4 SDS/Max 



Chloropropanone 

1,1-Dichloro- 

1,1,1-Trichloro- 

1-Bromo-1,1- 

1,1,3,3- 


propanone 

propanone 

dichloro- 

Tetrachloro- 




propanone 

propanone 


267 





















































Figure 33 


Formation and Stability of Haloacetaldehydes 
inSDS Testing (10/16/01) 

■ Plant 3 Eff m Plant 3 SDS/Ave 0 Plant 3 SDS/Max 

m Plant 4 Eff □ Plant 4 SDS/Ave 0 Plant 4 SDS/Max 

16 


14 

d 12 
"S> 

0 ) 10 

■o 

>* 

| 8 

re 

+-> 

o o 
o 6 
re 
o 

5 4 

2 


0 

Dichloroacetaldehyde Bromochloroacetaldehyde Chloral hydrate 



REFERENCES 

American Public Health Association (APHA,). Standard Methods for the Examination of Water 
and Wastewater, 20th ed. APHA, American Water Works Association, and Water Environment 
Federation: Washington, DC (1998). 

Baribeau, H., S. W. Krasner, R. Chinn, and P. C. Singer. Impact of biomass on the stability of 
haloacetic acids and trihalomethanes in a simulated distribution system. Proceedings of the 
American Water Works Association Water Quality Technology Conference, American Water 
Works Association: Denver, CO, 2000. 

Cowman, G. A., and P. C. Singer. Effect of bromide ion on haloacetic acid speciation resulting 
from chlorination and chloramination of aquatic humic substances. Environmental Science & 
Technology 30(1): 16 (1996). 

Environmental Engineering & Technology, Inc. (EE&T). Occurrence of, and Problems 
Associated With, Trace Contaminants in Water Treatment Chemicals. Progress report to 
AWWA Research Foundation, Denver, CO, 2000. 


268 














































Krasner, S. W., M. J. McGuire, J. G. Jacangelo, N. L. Patania, K. M. Reagan, and E. M. Aieta. 
The occurrence of disinfection by-products in US drinking water. Journal of the American 
Water Works Association 81 (8):41 (1989). 

Krasner, S. W., M. J. Sclimenti, and B. M. Coffey. Testing biologically active filters for 
removing aldehydes formed during ozonation. Journal of the American Water Works 
Association 85(5):62 (1993). 

Krasner, S. W., J. M. Symons, G. E. Speitel, Jr., A. C. Diehl, C. J. Hwang, R. Xia, and S. E. 
Barrett. Effects of water quality parameters on DBP formation during chloramination. 
Proceedings of the American Water Works Association Annual Conference, Vol. D, American 
Water Works Association: Denver, CO, 1996. 

Oliver, B. G. Dihaloacetonitriles in drinking water: algae and fulvic acid as precursors. 
Environmental Science & Technology 17(2):80 (1983). 

Simpson, K.L. and K. P. Hayes. Drinking watep'disinfection by-products: an Australian 
perspective. Water Research 32(5): 1522 (1^#8). 

Singer, P. C., H. Arora, E. Dundore, K. Brophy, and H. S. Weinberg. Control of haloacetic acid 
concentrations by biofiltration: a case study. Proceedings of the American Water Works 
Association Water Quality Technology Conference, American Water Works Association: 
Denver, CO, 1999. 

Stevens, A. A., L. A. Moore, and R. J. Miltner. Formation and control of non-trihalomethane 
disinfection by-products. Journal of the American Water Works Association 81 (8):54 (1989). 

Young, M. S., D. M. Mauro, P. C. Uden, and D. A. Reckhow. The formation of nitriles and 
related halogenated disinfection by-products in chlorinated and chloraminated water; application 
of microscale analytical procedures. Preprints of papers presented at 210th American Chemical 
Society National Meeting, Chicago, IL, American Chemical Society: Washington, D.C., pp. 
748-751, 1995. 


269 


EPA REGIONS 5 AND 7: PLANTS 9 AND 10 


Plant Operations and Sampling 

The Mississippi River is the source of water for many drinking-water-treatment plants 
(WTPs). Plant 10 (in EPA Region 5) treated water from the Mississippi River. In addition, plant 
9 (in EPA Region 7) treated water from the Mississippi River; however, the water that was 
treated at plant 9 was a combination of water from the Mississippi River and another river that 
flowed into the Mississippi. On January 10, 2001, April 9, 2001, August 27 or September 5, 
2001, November 26, 2001, and February 25, 2002, plant 10 and plant 9 were sampled. 

Plant 10 had two different treatment trains (Figure 1): 

• One train consisted of Aldrich purification units. Chlorine, alum, polymer, and powdered 
activated carbon (PAC) were added to the raw water. The water underwent flocculation, 
sedimentation, and filtration. Chlorine and ammonia were added to the filtered water to form 
chloramines in January and April 2001. Alternatively, chlorine and ammonia were both 
added to the raw water in November 2001 and February 2002 to form chloramines. During 
the September 2001 sampling, plant 10 used chlorine only. Many utilities that use 
chloramines switch back to the use of chlorine only once per year to control the growth of 
nitrifying bacteria in the distribution system. 

Figure 1. Schematic of treatment process at plant 10 



Distribution 


270 

























• The other train at plant 10 consisted of conventional treatment. PAC was applied to the raw 

water. Then within this train, there were parallel treatment basins: 

• Chlorine and alum were added at mixing tank number 2. Ammonia (to form 
chloramines) was added immediately after the mixing tank in January 2001, April 2001, 
and February 2002, but not during the September 2001 sampling. The water underwent 
sedimentation in basins 1 and 2. Basins 1 and 2 were out of service for repairs in 
November 2001. 

• (The raw water for basins 4 and 5 was a mixture of water from the two intakes, one for 
the Aldrich purification units and the other for the conventional treatment train.) 
Chlorine and alum were added at mixing tank number 1. No ammonia was added to this 
portion of the conventional train in January, April or September 2001. Alternatively, 
chlorine and ammonia were both added at mixing tank number 1 in November 2001 and 
February 2002 to form chloramines. Chlorinated (or chloraminated) water underwent 
flocculation and sedimentation (in basins number 4 and 5). 

• The water from all four settling basins was then filtered through granular activated 
carbon (GAC) filters. The GAC was operated for taste-and-odor control and not for the 
removal of DBP precursors. Chlorine and ammonia (to form chloramines) was added to 
the filtered water in January 2001, April 2001, November 2001, and February 2002, but 
not during the September 2001 sampling, when only chlorine was added. 

At plant 9 (Figure 2), initially, the water underwent pretreatment with polymer addition. 
Then the water was lime softened. The softened water was then chlorinated and treated with 
ferric sulfate [Fe 2 (S 04 ) 3 ] in the conditioning chamber. At the end of the conditioning chamber, 
ammonia was added to form chloramines. The water then passed through a series of settling 
basins. PAC was added to the effluent of basin #6. The water was then treated with additional 
ferric sulfate, polymer, chlorine, and ammonia. Finally, the water underwent filtration. 

Plant 10 was sampled at the following locations: 

Aldrich Purification Units Train 

(1) raw water 

(2) the filter effluent (January 2001 only) 

(3) the clearwell effluent 
Conventional Treatment Train 

(4) raw water 

(5) the effluent of basins 4 and 5 

(6) the effluent of basins 1 and 2 (except for November 2001) 

(7) the filter effluent 

(8) the clearwell effluent (January 2001 only) 

Combined Plant 

(9) the finished water 


271 






Finished Water 
Pumping Station 


Waste 

Washwater 


Clearwell 


Filters 


Secondary 
Sedimentaion 
Basins (9-7) 


Secondary 

Conditioning 

Basin 


PROCESS FLOW DIAGRAM 
PLANT 9 


Figure 2. Plant 9 water treatment plant 


272 
































































In addition, finished water from the point of entry was collected and simulated distribution 
system (SDS) testing was conducted for average and maximum detention times for that time of 
year (Table 1). In November 2001, a separate SDS sample at maximum detention time was 
prepared for the University of North Carolina (UNC), which used water from the clearwell of the 
conventional treatment train. Furthermore, the distribution system was sampled at one to two 
locations, one representing an average detention time and the other representing a maximum 
detention time (January 2001 only). 

Plant 9 was sampled at the following locations: 

(1) raw water 

(2) softened water 

(3) water from the primary conditioner 

(4) the effluent of basin #6 

(5) the filter influent 

(6) and the finished water 

In addition, finished water was collected and SDS testing was conducted for average and 
maximum detention times for that time of year (Table 1). Furthermore, the distribution system 
was sampled at two locations, one representing an average detention time and the other 
representing a maximum detention time. 


Table 1. SDS holding times at Mississippi River WTPs 


Sample 

1/10/01 

4/9/01 

8/27 or 
9/5/01 

11/26/01 

2/25/02 

Plant 10 average detention time 

4 hr 

4 hr 

4 hr 

4 hr 

4 hr 

Plant 10 maximum detention time 

5 days 

5 days 

5 days 

5 days 

5 days 

Plant 9 average detention time 

3 days 

3 days 

2 days 

2 days 

2 days 

Plant 9 maximum detention time 

6 days 

6 days 

3 days 

4 days 

3 days 


On the day of sampling, information was collected on the operations at each plant 
(Tables 2-3). 


Table 2. Operational information at plant 10 


Parameter 

1/10/01 

4/9/01 

9/5/01 

11/26/01 

2/25/02 

Aldrich Purification Units Train 






Plant flow for this train (mgd) 

8 

8 

11 

10 

8 

Chlorine dose at plant influent (mg/L as Cl 2 ) 

10 

17 

16 

10 

9.7 

Ammonia dose at plant influent (mg/L as NH 3 -N) 

0 

0 

0 

2.0 

1.7 

Alum dose at plant influent (mg/L) 

96 

96 

35 

60.4 

76.6 

Polymer dosage at plant influent (mg/L) 

3.7 

3.5 

2.1 a 

2.0 

3.5 

PAC dosage at plant influent (mg/L) 

1 

1.8 

0.5 

1.2 

3.0 

Permanganate dose at plant influent (mg/L) 

0 

0 

2.2 

0 

0 

Chlorine dose at combined filter eff. (mg/L as Cl 2 ) 

2 

1.6 

3.6 

0.8 

0 

NH 3 dose at combined filter eff. (mg/L as NH 3 -N) 

0.6 

0.8 

0 

0.8 

0 

Conventional Treatment Train 






PAC dosage at intake (mg/L) 

1 

1 

0.7 

0 

0 

Permanganate dose at intake (mg/L) 

0 

0 

2.0 

0 

1.7 


273 































Table 2 (continued) 


Parameter 

1/10/01 

4/9/01 

9/5/01 

11/26/01 

2/25/02 

Train for Basins 1 and 2 






Plant flow for these basins (mgd) 

10 

11 

11 

0 

8 

Chlorine dose at mixing tank no. 2 (mg/L as Cl 2 ) 

6 

6 

6.7 

— 

7.5 

NH 3 dose immediately after mixing tank no. 2 
(mg/L as NH 3 -N) 

1 

1 

0 

— 

1.5 

Alum dose at mixing tank number 2 (mg/L) 

54 

50 

53.2 

— 

51 

Train for Basins 4 and 5 






Plant flow for these basins (mgd) 

22 

20.6 

25.8 

27.5 

20.0 

Chlorine dose at mixing tank no. 1 (mg/L as Cl 2 ) 

6 

14 

9.1 

4.9 

5.7 

NH 3 dose at mixing tank no. 1 (mg/L as NH 3 -N) 

0 

0 

0 

0.9 

1.2 

Alum dose at mixing tank number 1 (mg/L) 

54 

50 

45.6 

55.4 

51 

Polymer dosage at mixing tank number 1 (mg/L) 

0 

1.1 

0 

0 

0 

Combined Conventional Treatment Train 






GAC filter loading rate (gpm/sq ft) 

NA b 

2 

2 

2 

2 

GAC empty bed contact time (min) 

NA 

5.6 

5.6 

5.6 

5.6 

Chlorine dose at combined filter eff. (mg/L as Cl 2 ) 

2 

3 

3.6 

3.7 

1.9 

NH 3 dose at combined filter eff. (mg/L as NH 3 -N) 

0.6 

0.6 

0 

0.7 

0.5 


a At intake 

= Not available 


Table 3. Operational information at plant 9 


Parameter 

1/10/01 

4/9/01 

8/27/01 

11/26/01 

2/25/02 

Plant flow (mgd) 

122 

88-94 

82 

70 

84 

Polymer dosage at plant influent (mg/L) 

1.0 

3.0 

2.0 

2.0 

2.5 

Lime dosage in softening basins (mg/L) 

108 

77 

101 

101 

103 

Chlorine dose at cond. chamber (mg/L as Cl 2 ) 

2.52 

2.3 

2.88 

2.16 

2.0 

Fe 2 (S0 4 ) 3 dose at conditioning chamber (mg/L) 

6.8 

6.8 

8.6 

3.4 

3.4 

Polymer dosage at conditioning chamber (mg/L) 

0.5 

1.5 

1.0 

1.0 

1.0 

NH 3 dose at end of cond. chamber (mg/L as NH 3 -N) 

1.44 

1.2 

1.92 

1.68 

1.6 

PAC dosage at Basin 6 effluent (mg/L) 

2.4 

6.0 

6.0 

1.2 

1.2 a 

Fe 2 (S0 4 ) 3 dose at influent to Basin 9 (mg/L) 

8.6 

6.8 

6.8 

3.4 

0 

Polymer dosage at influent to Basin 9 (mg/L) 

1.0 

0.4 

0.4 

0.4 

0 

Chlorine dose at influent to Basin 9 (mg/L as Cl 2 ) 

1.92 

2.9 

2.4 

2.16 

2.3 

Ammonia dose at inf. to Basin 9 (mg/L as NH 3 -N) 

1.44 

1.6 

1.92 

1.8 

1.8 

Chlorine dose at clearwell effluent (mg/L as Cl 2 ) 

0 

0 

0.24 

0 

0 

Ammonia dose at clearwell eff. (mg/L as NH 3 -N) 

0 

0 

0.12 

0 

0 


a PAC dosage at Basin 1 influent 


Water Quality 

On the day of sampling, information was collected on water quality at each plant 
(Tables 4-5). Data were collected for total organic carbon (TOC) and ultraviolet (UV) 
absorbance (Tables 6-7). The raw water in January 2001, April 2001, summer (August or 
September) 2001, November 2001, and February 2002 at plant 10 was somewhat higher in TOC 
than at plant 9 (4.0-5.9 versus 3.4-5.0 mg/L). Nonetheless, both utilities had a moderate loading 
of DBP precursors. 


274 














































At plant 10, in the Aldrich purification units in January 2001, April 2001, September 
2001, November 2001, and February 2002, 14-32 % of the TOC and 18-47 % of the UV was 
removed. At plant 10, in the conventional treatment train in January 2001, April 2001, 
September 2001, November 2001, and February 2002, coagulation removed 17-27 % of the TOC 
and filtration removed another 2-17 %. The overall TOC removal in the conventional treatment 
train was 28-34 %. In addition, the overall UV removal in the conventional treatment train was 
41-62%. 


At plant 9, in April 2001, August 2001, November 2001, and February 2002, softening 
removed 19-28 % of the TOC, whereas in January 2001 no TOC was initially removed during 
the softening process. At plant 9, with downstream coagulation and filtration, the overall TOC 
removal on these three sample dates was 17-34 %. In addition, the overall UV removal was 11- 
45 %. 


Tables 8-9 show the values of miscellaneous other water quality parameters in the raw 
water at plant 10 and plant 9, respectively. The raw water in January 2001, April 2001, summer 
(August or September) 2001, November 2001, and February 2002 at plant 9 was higher in 
bromide than at plant 10 (0.06-0.36 versus 0.05-0.08 mg/L). Nonetheless, both utilities had a 
moderate loading of inorganic DBP precursors. 


275 


Table 4. Water quality information at plant 10 



pH 

Temperature (°C) 

Disinfectant Residual* (mg/L) 

Location 

1/10/01 

4/9/01 

9/5/01 

11/26/01 

2/25/02 

1/10/01 

4/9/01 

9/5/01 

11/26/01 

2/25/02 

1/10/01 

4/9/01 

9/5/01 

11/26/01 2/25/02 

Aldrich Purification Units Train 

Raw water 

8.01 

8.32 

8.21 

8.5 

8.67 

1.5 

13.1 

28.1 

13.3 

7.5 

— 

— 

— 

— 

— 

Filter eff. 

7.67 

7.51 

7.39 

7.8 

7.84 

2.7 

14.7 

29.8 

14.2 

8.2 

1.3 

2.4 

2.1 

5.4 

5.0 

Clearwell 

7.56 

7.50 

7.60 

7.6 

7.70 

— 

14.9 

28.4 

13.5 

9.5 

3.7 

4.2 

4.0 

5.6 

4.9 

Conventional Treatment Train 

Raw water 

8.03 

8.38 

8.33 

8.5 

8.68 

0.7 

13.3 

28.0 

14.7 

6.4 

— 

— 

— 

— 

— 

Basins 4&5 

7.38 

7.36 

7.24 

7.8 

7.79 

0.3 

14.0 

29.2 

16.1 

5.8 

1.9 

3.3 

2.4 

3.3 

5.3 

Basins 1&2 

7.49 

7.47 

7.22 

NS 

7.80 

0.4 

14.1 

27.4 

NS 

5.6 

4.7 

4.1 

0.7 

NS 

3.9 

Filter eff. 

7.37 

7.37 

7.16 

7.6 

7.75 

3.5 

14.7 

28.3 

13.2 

6.1 

0.3 b 

0.2 b 

0.4 

0.4 

1.1 

Clearwell 

7.45 

7.54 

7.70 

7.5 

7.64 

2.6 

15.0 

28.0 

13.1 

7.9 

3.2 

3.6 

3.4 

3.8 

3.6 

Combined Plant 

Finished 

7.48 

7.41 

7.68 

7.5 

7.69 

3.0 

14.4 

27.5 

12.3 

6.5 

3.7 

3.7 

3.5 

3.4 

3.6 

DS c /ave 

7.53 

7.48 

7.54 

7.4 

7.38 

2.4 

13.1 

26.4 

13.5 

7.4 

2.4 

3.3 

3.1 

3.1 

3.0 

DS/max 

7.47 

NS d 

NS 

NS 

NS 

10.4 

NS 

NS 

NS 

NS 

1.7 

NS 

NS 

NS 

NS 

SDS/ave 

7.51 

7.46 

7.63 

7.5 

7.65 

2.9 

14.8 

27.6 

12.2 

6.3 

3.5 

3.5 

2.9 

3.2 

3.0 

S DS/max 

7.52 

7.39 

7.56 

7.5 

7.57 

2.5 

15.3 

26.4 

11.8 

5.6 

2.9 

1.8 

0.3 

0.9 

2.3 

SDS/max 
for UNC 

— 

— 

— 

7.5 


— 

— 

— 

11.5 

— 

— 

— 

— 

1.0 

— 


a Chlorine residuals (values shown in italics) at Basins 4 & 5 effluent in January and April 2001, and all sample locations in September 2001; chloramine 
residuals at other locations. 
b GAC filters removed chlorine. 

C DS = Distribution system 
d NS = Not sampled 


276 



















































































Table 5. Water quality information at plant 9 



pH 

Temperature (°C) 

Disinfectant Residual 3 (mg/L) 

Location 

1/10/01 

4/9/01 

8/27/01 

11/26/01 

2/25/02 

1/10/01 

4/9/01 

8/27/01 

11/26/01 

2/25/02 

1/10/01 

4/9/01 

8/27/01 

11/26/01 

2/25/02 

Raw 

8.10 

8.00 

8.64 

8.26 

8.24 

1.1 

14.4 

28.3 

12.8 

8.3 

— 

— 

— 

— 

— 

Softened 

9.97 

10.2 

9.82 

10.1 

9.37 

1.5 

14.4 

27.0 

13.3 

8.6 

— 

— 

— 

— 

— 

1° cond. 

9.74 

9.85 

9.66 

9.97 

9.35 

1.4 

15.6 

26.9 

13.3 

8.6 

1.60 

1.50 

1.10 

2.20 

1.60 

Basin #6 

9.66 

9.68 

9.76 

9.65 

9.32 

2.2 

15.6 

26.1 

13.3 

9.4 

1.60 

1.10 

0.95 

1.50 

1.55 

Filter inf. 

9.21 

9.31 

9.34 

9.39 

9.12 

2.2 

15.6 

26.7 

14.4 

9.8 

2.50 

2.25 

2.25 

2.65 

2.60 

Finished 

9.59 

9.70 

9.23 

9.35 

9.12 

1.4 

15.6 

27.2 

13.3 

8.9 

2.45 

2.25 

2.40 

2.65 

2.60 

DS/ave 

9.74 

9.35 

9.15 

9.10 

9.23 

3.7 

18.9 

28.0 

13.1 

9.8 

2.45 

2.15 

2.25 

2.30 

2.55 

DS/max 

9.48 

9.33 

9.38 

9.20 

9.28 

4.0 

18.9 

28.4 

13.2 

9.8 

2.40 

2.15 

2.10 

2.20 

2.40 

SDS/ave 

9.18 

9.26 

9.19 

9.36 

8.93 

8.9 

16.0 

24.4 

15.6 

7.8 

2.45 

2.20 

2.20 

2.40 

2.45 

S DS/max 

9.09 

9.26 

9.29 

9.38 

8.9 

6.7 

16.5 

25.0 

13.9 

7.2 

2.35 

2.10 

2.10 

2.30 

2.4 


“Chlorine residuals (values shown in italics) at primary (1°) conditioner in January, April, and August 2001; chloramine residuals at other locations. 


277 






























Table 6. TOC and UV removal at plant 10 


Location 

TOC 

(mg/L) 

UV a 

(cm' 1 ) 

SUVA 6 

(L/mg-m) 

Removal/Unit (%) 

Removal/Cumulative (%) 

TOC 

UV 

TOC 

UV 

01/10/2001 








Aldrich Raw 

4.83 

0.113 

2.34 

— 

— 

— 

— 

Aldrich Filter Eff. 

3.57 

0.063 

1.76 

26% 

44% 

26% 

44% 

Conventional Raw 

5.11 

0.127 

2.49 

— 

— 

— 

— 

Basins 4 & 5 Eff. 

4.12 

0.057 

1.38 

19% 

55% 

19% 

55% 

Basins 1 & 2 Eff. 

4.04 

0.079 

1.96 

21% 

38% 

21% 

38% 

Combined Filter Eff. c 

3.42 

0.053 

1.55 

17% 

7.0% 

33% 

58% 

04/09/2001 








Aldrich Raw 

4.01 

0.093 

2.32 

— 

— 

— 

— 

Aldrich Clearwell Eff. 

2.86 

0.051 

1.78 

29% 

45% 

29% 

45% 

Conventional Raw 

4.22 

0.103 

2.44 

— 

— 

— 

— 

Basins 4 & 5 Eff. 

3.08 

0.035 

1.14 

27% 

66% 

27% 

66% 

Basins 1 & 2 Eff. 

3.11 

0.053 

1.70 

26% 

49% 

26% 

49% 

Combined Filter Eff. 

3.03 

0.039 

1.29 

1.6% 

-11% 

28% 

62% 

09/05/2001 








Aldrich Raw 

5.45 

0.148 

2.72 

— 

— 

— 

— 

Aldrich Clearwell Eff. 

4.68 

0.078 

1.67 

14% 

47% 

14% 

47% 

Conventional Raw 

5.87 

0.152 

2.59 

— 

— 

— 

— 

Basins 4 & 5 Eff. 

4.39 

0.066 

1.50 

25% 

57% 

25% 

57% 

Basins 1 & 2 Eff. 

4.89 

0.075 

1.53 

17% 

51% 

17% 

51% 

Combined Filter Eff. 

4.22 

0.067 

1.59 

3.9% 

-1.5% 

28% 

56% 

11/26/2001 








Aldrich Raw 

4.98 

0.122 

2.45 

— 

— 

— 

— 

Aldrich Clearwell Eff. 

3.64 

0.100 

2.75 

27% 

18% 

27% 

18% 

Conventional Raw 

5.04 

0.127 

2.52 

— 

— 

— 

— 

Basins 4 & 5 Eff. 

4.0 

0.089 

2.23 

21% 

30% 

21% 

30% 

Basins 1 & 2 Eff. 

NS 

NS 

— 

— 

— 

— 

— 

Combined Filter Eff. 

3.43 

0.070 

2.04 

14% 

21% 

32% 

45% 

02/25/2002 








Aldrich Raw 

4.52 

0.099 

2.19 

— 

— 

— 

— 

Aldrich Clearwell Eff. 

3.08 

0.075 

2.44 

32% 

24% 

32% 

24% 

Conventional Raw 

4.91 

0.111 

2.26 

— 

— 

— 

— 

Basins 4 & 5 Eff. 

3.67 

0.083 

2.26 

25% 

25% 

25% 

25% 

Basins 1 & 2 Eff. 

3.57 

0.072 

2.02 

27% 

35% 

27% 

35% 

Combined Filter Eff. 

3.24 

0.065 

2.01 

12% 

22% 

34% 

41% 


a UV = Ultraviolet absorbance reported in units of "inverse centimeters" (APHA, 1998) 
b SUVA (L/mg-m) = Specific ultraviolet absorbance = 100*UV (cm'^/DOC (mg/L) or UV (m'^/DOC (mg/L), 
where DOC = dissolved organic carbon, which typically = 90-95% TOC (used TOC values in calculating SUVA) 
(e.g., UV = 0.113/cm = 0.113/(0.01 m) = 11.3/m, DOC = 4.83 mg/L, SUVA = (11.3 m')l{4.83 mg/L) = 2.34 L/mg-m) 
c Remova!/unit compared to basins 4 & 5 effluent 


278 
















































Table 7. TOC and UV removal at plant 9 


Location 

TOC 

(mg/L) 

UV a 

(cm' 1 ) 

SUVA b 

(L/mg-m) 

Rem ova 

/Unit (%) 

Removal/Cumulative (%) 

TOC 

UV 

TOC 

UV 

01/10/2001 








Raw 

3.39 

0.063 

1.86 

— 

— 

— 

— 

Softened Water 

3.51 

0.049 

1.40 

-3.5% 

22% 

-3.5% 

22% 

Primary Conditioner 

3.09 

0.055 

1.78 

12% 

-12% 

8.8% 

13% 

Basin #6 Eff. 

3.20 

0.056 

1.75 

-3.6% 

-1.8% 

5.6% 

11% 

Filter Inf. 

2.85 

0.059 

2.07 

11% 

-5.4% 

16% 

6.3% 

Finished Water 

2.80 

0.056 

2.00 

1.8% 

5.1% 

17% 

11% 

04/09/2001 








Raw 

4.96 

0.137 

2.76 

— 

— 

— 

— 

Softened Water 

3.58 

0.076 

2.12 

28% 

45% 

28% 

45% 

Primary Conditioner 

3.61 

0.078 

2.16 

-0.8% 

-2.6% 

27% 

43% 

Basin #6 Eff. 

4.05 

0.089 

2.20 

-12% 

-14% 

18% 

35% 

Filter Inf. 

3.51 

0.078 

2.22 

13% 

12% 

29% 

43% 

Finished Water 

3.49 

0.076 

2.18 

0.6% 

2.6% 

30% 

45% 

08/27/2001 








Raw 

4.22 

0.093 

2.20 

— 

— 

— 

— 

Softened Water 

3.40 

0.068 

2.00 

19% 

27% 

19% 

27% 

Primary Conditioner 

3.19 

0.052 

1.63 

6.2% 

24% 

24% 

44% 

Basin #6 Eff. 

2.97 

0.058 

1.95 

6.9% 

-12% 

30% 

38% 

Filter Inf. 

2.79 

0.056 

2.01 

6.1% 

3.4% 

34% 

40% 

Finished Water 

2.77 

0.058 

2.09 

0.7% 

-3.6% 

34% 

38% 

11/26/2001 








Raw 

3.61 

0.082 

2.27 

— 

— 

— 

— 

Softened Water 

2.69 

0.047 

1.75 

25% 

43% 

25% 

43% 

Primary Conditioner 

2.89 

0.054 

1.87 

-7.4% 

-15% 

20% 

34% 

Basin #6 Eff. 

2.43 

0.050 

2.06 

16% 

7% 

33% 

39% 

Filter Inf. 

2.29 

0.051 

2.23 

5.8% 

-2.0% 

37% 

38% 

Finished Water 

2.37 

0.053 

2.24 

-3.5% 

-3.9% 

34% 

35% 

02/25/2002 








Raw 

3.37 

0.074 

2.20 

— 

— 

— 

— 

Softened Water 

2.67 

0.049 

1.84 

21% 

34% 

21% 

34% 

Primary Conditioner 

3.34 

0.050 

1.50 

-25% 

-2.0% 

1% 

32% 

Basin #6 Eff. 

2.50 

0.051 

2.04 

25% 

-2.0% 

26% 

31% 

Filter Inf. 

2.55 

0.054 

2.12 

-2.0% 

-5.9% 

24% 

27% 

Finished Water 

2.48 

0.055 

2.22 

2.7% 

-1.9% 

26% 

26% 


a UV = Ultraviolet absorbance reported in units of "inverse centimeters" (APHA, 1998) 
b SUVA (L/mg-m) = Specific ultraviolet absorbance = 100*UV (cm'^/DOC (mg/L) or UV (m'^/DOC (mg/L), 
where DOC = dissolved organic carbon, which typically = 90-95% TOC (used TOC values in calculating SUVA) 
(e.g., UV = 0.063/cm = 0.063/(0.01 m) = 6.3/m, DOC = 3.39 mg/L, SUVA = (6.3 m'V(3.39 mg/L) = 1.86 L/mg-m) 


On the January 2001, April 2001, September 2001, November 2001, and February 2002 
samplings, the raw water at plant 10 contained up to 0.16 mg/L of ammonia (Table 8). 
Theoretically, it takes 7.6 mg/L of chlorine to breakpoint chlorinate 1.0 mg/L of ammonia- 
nitrogen. The theoretical inorganic chlorine demand (up to 1.2 mg/L) was significantly less than 
the initial chlorine dose applied at each of the trains when prechlorination was practiced (6-17 
mg/L) (Table 2). 


279 

















































Table 8. Miscellaneous water quality parameters in raw water at plant 10 


Location 

Bromide 

(mg/L) 

Alkalinity 

(mg/L) 

Ammonia 
(mg/L as N) 

Chlorine 
Demand 3 (mg/L) 

01/10/2001 





Aldrich Train Raw 

0.08 

199 

0.15 

1.1 

Conventional Train Raw 

0.07 

199 

0.16 

1.2 

04/09/2001 





Aldrich Train Raw 

0.05 

176 

ND b 

0 

Conventional Train Raw 

0.05 

173 

0.08 

0.6 

09/05/2001 





Aldrich Train Raw 

0.07 

148 

0.04 

0.3 

Conventional Train Raw 

0.07 

149 

ND 

0 

11/26/2001 





Aldrich Train Raw 

0.05 

189 

0.05 

0.4 

Conventional Train Raw 

0.05 

186 

0.07 

0.5 

02/25/2002 





Aldrich Train Raw 

0.05 

175 

0.06 

0.5 

Conventional Train Raw 

0.05 

188 

0.14 

1.1 


a Chlorine demand from ammonia = 7.6 * ammonia (mg/L as N) 
b ND = Not detected 


Table 9. Miscellaneous water quality parameters in raw water at plant 9 


Date 

Bromide 

(mg/L) 

Alkalinity 

(mg/L) 

Ammonia 
(mg/L as N) 

Chlorine 
Demand 3 (mg/L) 

01/10/2001 

0.19 

221 

0.37 

2.8 

04/09/2001 

0.06 

99 

0.05 

0.4 

08/27/2001 

0.1 

175 

ND 

0 

11/26/2001 

0.2 

182 

0.07 

0.5 

02/25/2002 

0.36 

171 

0.1 

0.8 


a Chlorine demand from ammonia = 7.6 * ammonia (mg/L as N) 


In January 2001, the raw water at plant 9 contained 0.4 mg/L of ammonia, whereas in 
April 2001, August 2001, November 2001, and February 2002 it only had up to 0.1 mg/L of 
ammonia (Table 9). The theoretical inorganic chlorine demand in January 2001 (2.8 mg/L) was 
somewhat higher than the initial chlorine dose applied at the conditioning chamber (2.5 mg/L) 
(Table 3). Alternatively, the theoretical inorganic chlorine demand in February 2002 (0.8 mg/L) 
was lower than the initial chlorine dose applied at the conditioning chamber (2.0 mg/L). 


280 

































DBPs 


Tables 10 and 11 (1/10/01), Tables 13 and 14 (4/9/01), Tables 16 and 17 (8/27-9/5/01), 
Tables 18 and 19 (11/26/01), and Tables 22 and 23 (2/25/02) show results for the halogenated 
organic DBPs that were analyzed for at Metropolitan Water District of Southern California 
(MWDSC). Table 12 (1/10/01) and Table 20 (11/26/01) show results for additional target DBPs 
that were analyzed for at UNC. Table 20 (11/26/01) show results for halogenated furanones that 
were analyzed for at UNC. Table 15 (4/9/01 [plant 10], 8/27/01 [plant 9], and 2/25/02 [plant 
10]) shows results from broadscreen analyses conducted at the U.S. Environmental Protection 
Agency (USEPA). 


Summary of Tables for DBPs for Mississippi River WTPs 


DBP Analyses (Laboratory) 

1/10/01 

4/9/01 

8/27 or 
9/5/01 

11/26/01 

2/25/02 

Halogenated organic DBPs (MWDSC) 

Tables 10- 
11 

Tables 13- 
14 

Tables lb- 
17 

Tables 18- 
19 

Tables 22- 
23 

Additional target DBPs (UNC) 

Table 12 



Table 20 


Halogenated furanones (UNC) 




Table 21 


Broadscreen analysis (USEPA) 


Table 15 a 

Table 15 b 


Table 15 a 


a Plant 10 
b Plant 9 


Halomethanes . Chlorine and/or chloramine disinfection at plant 10 in January and April 
2001 resulted in the formation of 71-84 and 54 pg/L of the four regulated trihalomethanes 
(THM4) in the Aldrich purification units and in basins 4 and 5, respectively. THM formation 
was lower in the effluent of basins 1 and 2 in January (30 pg/L of chloroform) and April 2001 
(31 pg/L of THM4) because free chlorine was only present in mixing tank number 2 before 
ammonia addition (upstream of basins 1 and 2). Chlorine only disinfection in September 2001 
resulted in the formation of 144, 144, and 174 pg/L of THM4 in the Aldrich purification units, in 
basins 4 and 5, and in basins 1 and 2, respectively. Another major difference between the three 
seasons was temperature: 0.3-3°C in January 2001, 13-15°C in April 2001, and 26-30°C in 
September 2001 (Table 4). Thus, THM formation was significantly higher in September 2001 
due to the presence of only free chlorine (no chloramines) and the warmer water temperature. In 
contrast, the use of chloramines only at plant 10 in November 2001 and February 2002 resulted 
in the formation of 12-19 and 8-14 pg/L of THM4 in the Aldrich purification units and in basins 
4 and 5, respectively. 

Chlorine/chloramine disinfection at plant 9 in January 2001, April 2001, August 2001, 
November 2001, and February 2002 resulted in the formation of 6-8 pg/L of THM4. There was 
no seasonal variability in the concentration of THM4 at this plant during this time period. The 
very low concentration of THMs at plant 9 suggests that there was minimal free chlorine contact 
time prior to ammonia addition. 

Although there were large differences in the total amounts of THMs formed, both WTPs 
produced a high percentage of the THMs as chloroform, followed by bromodichloromethane, 
when the raw-water bromide was less than or equal to 0.1 mg/L. Figure 3 shows the impact of 


281 












bromide on THM speciation at plant 9. As the concentration of bromide increased, the formation 
of chloroform decreased and the formation of dibromochloromethane increased. 


Figure 3. Impact of bromide on THM speciation in finished water at plant 9 



0.06 
0.1 

0.19 Bromide 
0.2 (mg/L) 

0.36 


Dichloroiodomethane was detected at plant 10 in November 2001 and February 2002. 
Dichloroiodomethane, bromochloroiodomethane, and chlorodiiodomethane (February only) were 
detected at plant 9 in November 2001 and February 2002. Bromide was at its highest in the 
influent of plant 9 in the latter two months. In addition, two of the iodinated THMs were 
detected by the broadscreen gas chromatography/mass spectrometry (GC/MS) methods at both 
WTPs (dichloroiodomethane and bromochloroiodomethane; Table 15). 

Dibromomethane, a volatile organic compound (VOC), was detected (0.13 pg/L)— 
slightly above the minimum reporting level (MRL) (0.11 pg/L)—in a SDS sample of plant 9 in 
January 2001. In other research, this dihalogenated methane had been detected in a high- 
bromide water that had been disinfected with chloramines (Krasner et al., 1996). In addition, 
bromomethane was detected at its MRL (0.2 pg/L) in a plant 9 distribution system sample in 
November 2001. 


282 












Table 10. DBP results at plant 10 ( 


710/01) 


01/10/2001 

MRL a 

Aldrich b 

Conventional 13 

Combined Plant 13 

Compound 

Mg/L 

Raw 

Filt Eff 

Clearwell 

Raw 

Basins 4&5 

Basins 1&2 

Filt Eff 

Clearwell 

Finished 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Halomethanes 















Chloromethane 

0.15 

ND C 


ND 

ND 

ND 


ND 

ND 

ND 

ND 


ND 


Bromomethane 

0.20 

ND 


ND 

ND 

ND 


ND 

ND 

ND 

ND 


ND 


Bromochloromethane 

0.14 

ND 


ND 

ND 

ND 


ND 

ND 

ND 

ND 


ND 


Dibromomethane 

0.11 

ND 


ND 

ND 

ND 


ND 

ND 

ND 

ND 


ND 


Chloroform 13 

0.1 

0.1 

60 

60 

0.1 

40 

30 

45 

40 

45 

50 

60 

45 

60 

Bromodichloromethane d 

0.10 

ND 

NR e 

20 

0.1 

12 

NR 

13 

12 

13 

15 

NR 

14 

NR 

Dibromochloromethane d 

0.07 

ND 

NR 

4 

ND 

2 

NR 

2 

2 

2 

2 

NR 

2 

NR 

Bromoform d 

0.6 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

THM4 f 


0.1 

NR 

84 

0.2 

54 

NR 

60 

54 

60 

67 

NR 

61 

NR 

Dichloroiodomethane 

0.25 

ND 

NR 

ND 

ND 

ND 

NR 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

Bromochloroiodomethane 

0.20 

ND 

NR 

ND 

ND 

ND 

NR 

ND 

ND 

ND 

ND 

NR 

ND 

NR 

Dibromoiodomethane 

0.6 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.6 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.14 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 

ND 


0.3 

ND 

ND 


ND 

ND 

0.07 

0.1 


0.08 


Halnar-ptin acids 















Monochloroacetic acid d 

2 


10 

10 


8.8 

1.3 

7.8 

6.5 

6.0 

6.9 


7.2 


Monobromoacetic acid d 

1 


1.0 

ND 


ND 

ND 

ND 

ND 

ND 

ND 


ND 


Dichloroacetic acid d 

1 


29 

29 


24 

19 

21 

23 

24 

24 


24 


Bromochloroacetic acid d 

1 


6.1 

6.0 


4.6 

3.7 

4.4 

4.9 

5.1 

5.1 


4.8 


Dibromoacetic acid d 

1 


1.0 

1.0 


ND 

ND 

ND 

ND 

ND 

ND 


ND 


Trichloroacetic acid d 

1 


54 

55 


44 

22 

45 

40 

43 

44 


35 


Bromodichloroacetic acid 

1 


11 

10 


9.1 

5.3 

9.2 

8.5 

9.1 

8.8 


8.2 


Dibromochloroacetic acid 

1 


1.7 

1.7 


1.4 

1.0 

1.3 

1.2 

1.4 

1.4 


1.0 


Tribromoacetic acid 

2 


ND 

ND 


ND 

ND 

ND 

ND 

ND 

ND 


ND 


HAA5 9 



95 

95 


77 

42 

74 

70 

73 

75 


66 


HAA9 h 



114 

113 


92 

52 

89 

84 

89 

90 


80 


DXAA 1 



36 

36 


29 

23 

25 

28 

29 

29 


29 


TXAA 1 



67 

67 


55 

28 

56 

50 

54 

54 


44 


Hainar.fttnnitrilft.s 















Chloroacetonitrile 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.10 

ND 

ND 

1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.10 

ND 

4 

4 

ND 

3 

2 

2 

2 

2 

3 

3 

2 

3 

Bromochloroacetonitrile d 

0.10 

ND 

2 

2 

ND 

1 

0.5 

0.5 

0.6 

0.7 

0.9 

1 

0.7 

1 

Dibromoacetonitrile d 

0.10 

ND 

0.2 

0.2 

ND 

0.1 

ND 

ND 

ND 

0.1 

0.1 

0.1 

0.1 

0.1 

T richloroacetonitrile a 

0.10 

ND 

0.5 

0.6 

0.1 

ND 

0.2 

0.4 

0.3 

0.4 

0.4 

ND 

ND 

ND 

Halnkptnnps 















Chloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

0.2 

0.2 

ND 

ND 

ND 

ND 

1,1 -Dichloropropanone d 

0.10 

ND 

1 

1 

ND 

0.9 

1 

0.7 

0.8 

0.8 

0.9 

1 

0.8 

1 

1,3-Dichloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

N/A 



NR 

NR 

NR 


NR 

NR 

NR 

NR 


NR 


1,1,1 -T richloropropanone d 

0.10 

ND 

4 

4 

ND 

3 

2 

3 

3 

3 

3 

3 

3 

3 

1,1,3-T richloropropanone 

0.10 

ND 

0.1 

0.1 

ND 

0.1 

0.1 

0.1 

0.1 

0.1 

0.2 

0.2 

0.1 

0.1 

1 -Bromo-1,1 -dichloropropanone 

N/A 



NR 

NR 

NR 


NR 

NR 

NR 

NR 


NR 


1,1,1 -Tri bromopropanone 

N/A 



NR 

NR 

NR 


NR 

NR 

NR 

NR 


NR 


1,1,3-T ribromopropanone 

N/A 



NR 

NR 

NR 


NR 

NR 

NR 

NR 


NR 


1,1,3,3-T etrachloropropanone 

0.10 

ND 

0.6 

0.3 

ND 

0.4 

0.3 

0.2 

0.2 

0.2 

0.2 

0.3 

0.4 

0.3 

1,1,3,3-Tetrabromopropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetaldehydes 















Dichloroacetaldehyde 

0.16 

ND 

5 

5 

ND 

4 

2 

4 

4 

4 

4 

4 

4 

5 

Bromochloroacetaldehyde 

0.10 

ND 

1 

1 

ND 

1 

1 

0.9 

1 

1 

1 

2 

1 

2 

Chloral hydrate 13 

0.10 

ND 

4 

5 

ND 

3 

1 

2 

3 

3 

4 

4 

3 

4 

T ribromoacetaldehyde 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 















Bromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

N/A 



NR 

NR 

NR 


NR 

NR 

NR 

NR 


NR 


Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 

0.10 

ND 

1 

1 

ND 

0.8 

0.9 

0.8 

0.8 

0.8 

0.9 

1 

0.8 

1 

Miscellaneous ComDounds 















Methyl ethyl ketone 

N/A 

NR 


NR 

NR 

NR 


NR 

NR 

NR 

NR 


NR 


Methyl tertiary butyl ether 

0.16 

ND 


ND 

ND 

ND 


ND 

ND 

ND 

ND 


ND 


Benzyl chloride 

N/A 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

NR 


283 


























































































Table 11. DBP results at Plant 9 (1/10/01) 


01/10/2001 

mrI7 

Plant 9 k 

Compound 

pg/L 

Raw 

1 u Cond 

Basin #6 

Filt Inf 

Finished 

DS/Ave 

DS/Max 

S DS/Ave 

S DS/Max 

Halomethanes 











Chloromethane 

0.15 

ND C 

ND 

ND 


ND 

ND 


ND 


Bromomethane 

0.20 

ND 

ND 

ND 


ND 

ND 


ND 


Bromochloromethane 

0.14 

ND 

ND 

ND 


ND 

ND 


ND 


Dibromomethane 

0.11 

ND 

ND 

ND 


ND 

ND 


0.13 


Chloroform' 1 

0.1 

ND 

1 

2 

3 

3 

3 

3 

3 

3 

Bromodichloromethane 3 

0.10 

0.1 

0.5 

0.7 

NR e 

2 

2 

NR 

2 

NR 

Dibromochloromethane d 

0.07 

ND 

0.2 

0.3 

NR 

0.8 

1 

NR 

1 

NR 

Bromoform d 

0.6 

ND 

ND 

ND 

ND 

0.7 

1 

1 

0.7 

0.8 

THM4 f 


0.1 

2 

3 

NR 

7 

7 

NR 

7 

NR 

Dichloroiodomethane 

0.25 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloroiodomethane 

0.20 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromoiodomethane 

0.6 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.6 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.14 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 

ND 

ND 

ND 


ND 

ND 


ND 


Halnar.atir arirl<; 











Monochloroacetic acid d 

2 


ND 

ND 


ND 

ND 


ND 


Monobromoacetic acid d 

1 


ND 

ND 


ND 

ND 


ND 


Dichloroacetic acid d 

1 


2.2 

2.5 


3.1 

3.4 


3.5 


Bromochloroacetic acid d 

1 


1.0 

1.1 


1.4 

1.6 


1.5 


Dibromoacetic acid d 

1 


1.0 

1.2 


1.3 

1.7 


1.5 


Trichloroacetic acid d 

1 


ND 

ND 


ND 

ND 


ND 


Bromodichloroacetic acid 

1 


ND 

ND 


ND 

ND 


ND 


Dibromochloroacetic acid 

1 


ND 

ND 


ND 

ND 


ND 


Tribromoacetic acid 

2 


ND 

ND 


ND 

ND 


ND 


HAA5 9 



3.2 

3.7 


4.4 

5.1 


5.0 


HAA9 h 



4.2 

4.8 


5.8 

6.7 


6.5 


DXAA 1 



4.2 

4.8 


5.8 

6.7 


6.5 


TXAA* 



ND 

ND 


ND 

ND 


ND 


Haloacetonitriles 











Chloroacetonitrile 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.10 

ND 

0.1 

0.1 

0.3 

0.3 

0.3 

0.2 

0.2 

0.1 

Bromochloroacetonitrile d 

0.10 

ND 

ND 

ND 

0.1 

0.1 

0.2 

0.1 

0.1 

0.1 

Dibromoacetonitrile d 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

T richloroacetonitrile 0 

0.10 

ND 

0.1 

0.1 

0.1 

ND 

ND 

ND 

ND 

ND 

Haloketones 











Chloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dichloropropanone d 

0.10 

ND 

0.3 

0.3 

0.2 

0.2 

0.2 

0.2 

0.2 

0.2 

1,3-Dichloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

N/A 

NR 

NR 

NR 


NR 

NR 


NR 


1,1,1 -T richloropropanone d 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-T richloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

N/A 

NR 

NR 

NR 


NR 

NR 


NR 


1,1,1-Tribromopropanone 

N/A 

NR 

NR 

NR 


NR 

NR 


NR 


1,1,3-T ribromopropanone 

N/A 

NR 

NR 

NR 


NR 

NR 


NR 


1,1,3,3-Tetrachloropropanone 

0.10 

0.2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrabromopropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetaldehydes 











Dichloroacetaldehyde 

0.16 

ND 

ND 

0.5 

0.6 

0.6 

0.6 

0.8 

0.9 

1 

Bromochloroacetaldehyde 

0.10 

ND 

0.3 

0.1 

0.1 

ND 

ND 

ND 

ND 

ND 

Chloral hydrate d 

0.10 

ND 

0.2 

0.2 

0.5 

0.5 

0.5 

0.3 

0.2 

0.1 

T ribromoacetaldehyde 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 











Bromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

N/A 

NR 

NR 

NR 


NR 

NR 


NR 


Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 3 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Miscellaneous ComDounds 











Methvl ethvl ketone 

N/A 

NR 

NR 

NR 


NR 

NR 


NR 


Methvl tertiarv butvl ether 

0.16 

0.3 

ND 

ND 


ND 

0.3 


ND 


Benzyl chloride 

N/A 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

NR 

NR 


k Plant 9 sampled at (1) raw water, (2) primary conditioner, (3) basin #6 effluent, (4) filter influent, 
(5) finished water, distribution system (DS) at (6) average and at (7) maximum detention times, 
and SDS testing of finished water at (8) average and at (9) maximum detention times 


284 






















































































a MRL = Minimum reporting level, which equals method detection limit (MDL) 
or lowest calibration standard or concentration of blank 

b Plant 10 sampled at train for Aldrich Purification units at (1) raw water, (2) filter influent, and (3) clearwell effluent; 

at conventional treatment train at (4) raw water, (5) basins 4&5 effluent, (6) basins 1&2 effluent, (7) combined filter effluent, and (8) clearwell effluent; 
and for combined treated waters at (9) finished water, distribution system (DS) at (10) average and at (11) maximum detention times, 
and SDS testing of finished water at (12) average and at (13) maximum detention times 
C ND = Not detected at or above MRL 

a DBP in the Information Collection Rule (ICR) (note: some utilities collected data for all 9 
haloacetic acids for the ICR, but monitoring for only 6 haloacetic acids was required) 
e NR = Not reported, due to interference problem on gas chromatograph or to problem with quality assurance 
( THM4 = Sum of 4 THMs (chloroform, bromodichloromethane, dibromochloromethane, bromoform) 

9 HAA5 = Sum of 5 haloacetic acids (monochloro-, monobromo-, dichloro-, dibromo-, trichloroacetic acid) 
h HAA9 = Sum of 9 haloacetic acids 

'DXAA = Sum of dihaloacetic acids (dichloro-, bromochloro-, dibromoacetic acid) 

’TXAA = Sum of trihaloacetic acids (trichloro-, bromodichloro-, dibromochoro-, tribromoacetic acid) 


Table 12. Additional target DBP results (ng/L) at Mississippi River WTPs (1/10/01) 


1/10/01 

Plant 9 a 

Plant 10 b 

Compound 

Raw 

PC 

PE 

DS 

SDS 

Raw 

B4&5 

B1&2 

FE 

PE 

Monochloroacetaldehyde 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.5 

0.8 

0.8 

0.4 

Dichloroacetaldehyde 

0.0 

0.0 

0.9 

0.9 

0.9 

0.0 

4.6 

3.9 

3.7 

3.6 

Bromochloroacetaldehyde 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.8 

2.0 

0.7 

1.3 

3,3-Dichloropropenoic acid 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.5 

0.4 

0.6 

0.8 

Bromochloromethylacetate 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

2,2-Dichloroacetamide 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

2.1 

1.5 

1.9 

1.7 

TOX (ng/L as Cl ) 

7.4 

58.7 

64.4 

55.7 

61.5 

13.7 

222 

252 

203 

237 

Cyanoformaldehyde 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

5-Keto-l-hexanal 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

6-Hydroxy-2-hexanone 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

Dimethylglyoxal 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

<0.4 

trans- 2-Hexenal 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 


a Plant 9 sampled at (1) raw water, (2) primary conditioner (PC), (3) finished water at plant effluent (PE), 
(4) distribution system (DS) at average detention time, and (5) SDS at maximum detection time. 
b Plant 10 sampled at (1) raw water, (2) effluent of basins 4 and 5 (B4&5), (3) effluent of basins 1 and 2 
(B1&2), (4) filter effluent (FE), and (5) PE. 


285 





























Table 13. DBP results at plant 10 (4/9/01) 


04/9/2001 

MRU* 

Aldrich 1 

Conventional 1 

Combined Plant 1 

Compound 

pg/L 

Raw 

Clearwell 

Raw 

Basins 4&5 

Basins 1&2 

Filt Eff 

Finished 

DS/Ave 

SDS/Ave 

SDS/Max 

Halomethanes 












Chloromethane 

0.5 

ND C 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Bromomethane 

0.20 

ND 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Bromochloromethane 

0.14 

NO 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Dibromomethane 

0.11 

ND 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Chloroform 11 

0.1 

ND 

54 

ND 

40 

22 

46 

50 

45 

42 

54 

Bromodichloromethane d 

0.1 

ND 

15 

ND 

12 

8 

14 

10 

14 

13 

16 

Dibromochloromethane d 

0.1 

ND 

2 

ND 

2 

0.8 

2 

1 

2 

2 

2 

Bromoform d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

THM4' 


ND 

71 

ND 

54 

31 

62 

61 

61 

57 

72 

Dichloroiodomethane 

0.2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloroiodomethane 

0.20 

ND 

ND 

ND 

ND 

NR 

ND 

ND 

ND 

ND 

NR 

Dibromoiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 

ND 

0.12 

ND 

ND 


0.11 

0.10 

0.13 

0.10 


T ribromochloromefhane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 












Monochloroacetic acid d 

2 


13 


14 

4.0 

8.6 

7.5 

7.5 

7.8 


Monobromoacetic acid d 

1 


ND 


ND 

ND 

ND 

ND 

ND 

ND 


Dichloroacetic acid d 

1 


33 


36 

23 

21 

27 

25 

28 


Bromochloroacetic acid d 

1 


5.6 


6.5 

3.7 

3.0 

5.3 

4.8 

5.0 


Dibromoacetic acid d 

1 


ND 


ND 

ND 

ND 

ND 

ND 

ND 


Trichloroacetic acid d 

1 


37 


40 

24 

35 

37 

35 

36 


Bromodichloroacetic acid 

1 


13 


15 

5.1 

11 

12 

11 

12 


Dibromochloroacetic acid 

1 


1.9 


2.2 

1.1 

1.6 

1.8 

1.6 

1.6 


Tribromoacetic acid 

2 


ND 


ND 

ND 

ND 

ND 

ND 

ND 


HAA5 9 



83 


90 

51 

65 

72 

68 

72 


HAA9 h 



104 


114 

61 

80 

91 

85 

90 


DXAA' 



39 


43 

27 

24 

32 

30 

33 


TXAA J 



52 


57 

30 

48 

51 

48 

50 


Haloacetonitriles 












Chloroacetonitrile 

0.1 

ND 

0.5 

ND 

0.2 

ND 

0.2 

0.1 

0.3 

0.2 

0.3 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.10 

ND 

8 

ND 

7 

3 

3 

3 

4 

4 

4 

Bromochloroacetonitrile d 

0.1 

ND 

1 

ND 

1 

0.5 

0.5 

0.4 

0.7 

0.7 

1 

Dibromoacetonitrile d 

0.2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

T richloroacetonitrile 0 

0.1 

ND 

0.4 

ND 

0.2 

0.2 

0.3 

0.2 

0.3 

0.3 

0.1 

Haloketones 












Chloropropanone 

0.5 

ND 

0.8 

ND 

0.5 

ND 

0.7 

0.5 

0.9 

0.7 

0.6 

1,1-Dichloropropanone d 

0.10 

ND 

1 

ND 

0.9 

1 

0.6 

0.5 

1 

1 

2 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T richloropropanone d 

0.1 

ND 

6 

ND 

8 

2 

6 

3 

4 

5 

3 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

0.3 

ND 

ND 

ND 

ND 

ND 

1-Bromo-1,1-dichloropropanone 

0.1 

ND 

0.6 

ND 

0.8 

0.4 

0.5 

0.3 

0.4 

0.4 

ND 

1,1,1 -T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-Tribromopropanone 

0.14 

ND 

ND 

ND 

ND 

0.1 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrachloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-T etrachloropropanone 

0.10 

ND 

ND 

ND 

0.1 

0.1 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrabromopropanone 

0.6 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

H a 1 oa cet aldehydes 












Dichloroacetaldehyde 

0.22 

0.2 

2 

ND 

2 

2 

1 

1 

2 

2 

3 

Bromochloroacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

0.4 

ND 

ND 

ND 

ND 

0.2 

Chloral hydrate d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

0.2 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 












Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.5 

ND 

0.4 

ND 

0.4 

0.2 

0.3 

ND 

0.3 

0.3 

0.1 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin 0 

0.1 

ND 

2 

ND 

2 

2 

2 

2 

2 

2 

3 

Miscellaneous ComDounds 












Methyl ethvl ketone 

1.9 

ND 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Methyl tertiarv butyl ether 

0.16 

ND 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Benzyl chloride 

NA 

ND 

ND 

ND 

ND 

NR e 

ND 

ND 

ND 

ND 

NR 


'Plant 10 sampled at train for Aldrich Purification units at (1) raw water and (2) clearwell effluent; 

at conventional treatment train at (3) raw water, (4) basins 4&5 effluent, (5) basins 1&2 effluent, and (6) combined filter effluent; 
and for combined treated waters at (7) finished water and (8) DS at average detention time, 
and SDS testing of finished water at (9) average and at (10) maximum detention times 


286 





















































































Table 14. DBP results at Plant 9 (4/9/01) 


04/9/2001 

"mrU 

Plant 9 k 

Compound 

pg/L 

Raw 

1 u Cond 

Basin #6 

Filt Inf 

Finished 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Halomethanes 











Chloromethane 

0.15 

ND C 

ND 

ND 


ND 

ND 


ND 


Bromomethane 

0.20 

ND 

ND 

ND 


ND 

ND 


ND 


Bromochloromethane 

0.14 

ND 

ND 

ND 


ND 

ND 


ND 


Dibromomethane 

0.11 

ND 

ND 

ND 


ND 

ND 


ND 


Chloroform d 

0.1 

ND 

6 

5 

6 

6 

5 

6 

7 

7 

Bromodichloromethane d 

0.1 

ND 

1 

1 

2 

2 

3 

3 

3 

2 

Dibromochloromethane d 

0.1 

ND 

0.1 

ND 

0.3 

0.3 

0.4 

0.4 

0.3 

0.3 

Bromoform d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

THM4' 


ND 

7 

6 

8 

8 

8 

9 

10 

9 

Dichloroiodomethane 

0.2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloroiodomethane 

0.20 

ND 

ND 

ND 

NR e 

ND 

ND 

NR 

ND 

NR 

Dibromoiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.06 

ND 

ND 

ND 


ND 

ND 


ND 


T ribromochloromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 











Monochloroacetic acid d 

2 


ND 

ND 


ND 

ND 


ND 


Monobromoacetic acid d 

1 


ND 

ND 


ND 

ND 


ND 


Dichloroacetic acid d 

1 


11 

12 


15 

14 


18 


Bromochloroacetic acid d 

1 


1.4 

1.3 


2.9 

2.6 


2.4 


Dibromoacetic acid d 

1 


ND 

ND 


ND 

ND 


ND 


Trichloroacetic acid d 

1 


1.1 

1.3 


2.7 

2.1 


2.3 


Bromodichloroacetic acid 

1 


ND 

ND 


ND 

ND 


ND 


Dibromochloroacetic acid 

1 


ND 

ND 


ND 

ND 


ND 


Tribromoacetic acid 

2 


ND 

ND 


ND 

ND 


ND 


HAA5 9 



12 

13 


18 

16 


20 


HAA9 h 



14 

15 


21 

19 


23 


dxaa' 



12 

13 


18 

17 


20 


TXAA 1 



1.1 

1.3 


2.7 

2.1 


2.3 


Haloacetonitriles 











Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.10 

ND 

0.4 

ND 

0.3 

0.3 

0.1 

0.1 

0.1 

0.1 

Bromochloroacetonitrile d 

0.1 

ND 

ND 

ND 

0.1 

0.1 

0.1 

ND 

ND 

ND 

Dibromoacetonitrile d 

0.2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Trichloroacetonitrile 0 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloketones 











Chloropropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dichloropropanone d 

0.10 

ND 

0.7 

0.3 

0.4 

0.4 

0.2 

0.2 

0.1 

0.1 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T richloropropanone 

0.1 

ND 

0.1 

0.1 

ND 

0.4 

ND 

ND 

ND 

ND 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

0.3 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

0.1 

ND 

ND 

ND 

ND 

1,1,1-Tribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-T ribromopropanone 

0.14 

ND 

ND 

ND 

ND 

0.1 

ND 

ND 

ND 

ND 

1,1,3,3-T etrachloropropanone 

0.1 

ND 

ND 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-Tetrachloropropanone 

0.10 

ND 

ND 

0.1 

ND 

0.1 

ND 

ND 

ND 

ND 

1,1,3,3-T etrabromopropanone 

0.6 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetaldehydes 











Dichloroacetaldehyde 

0.22 

ND 

1 

2 

2 

3 

2 

2 

2 

2 

Bromochloroacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

0.2 

ND 

ND 

ND 

ND 

Chloral hydrate d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Tribromoacetaldehyde 

0.1 

ND 

ND 

0.1 

ND 

0.4 

ND 

ND 

ND 

ND 

Halonitromethanes 











Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.5 

ND 

0.1 

0.1 

0.1 

0.1 

0.2 

0.2 

0.2 

0.2 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin a 

0.1 

ND 

0.1 

ND 

0.2 

0.2 

0.1 

0.1 

0.1 

ND 

Miscellaneous Compounds 











Methyl ethyl ketone 

1.9 

ND 

ND 

ND 


ND 

ND 


ND 


Methyl tertiary butyl ether 

0.16 

ND 

ND 

ND 


ND 

ND 


ND 


Benzyl chloride 

NA 

ND 

ND 

ND 

NR 

ND 

ND 

NR 

ND 

NR 


287 



















































































Table 15. Occurrence of other DBPs a at Mississippi River WTPs: finished waters at plant 
effluents _ 



Plant 10 

Plant 9 

Compound 

4/9/01 

2/25/02 

8/27/01 

Halomethanes 

Bromodichloromethane b 

x 

X 

X 

Dibromochloromethane 

X 

X 

X 

Bromoform 

X 

- 

X 

Dichloroiodomethane 

X 

X 

X 

Bromochloroiodomethane 

X 

X 

X 

Haloacids 

Dichloroacetic acid 

X 

X 

X 

Bromochloroacetic acid 

X 

X 

X 

Dibromoacetic acid 

- 

- 

X 

Bromodichloroacetic acid 

X 

- 

- 

Trichloroacetic acid 

X 

X 

- 

3,4,4-Trichloro-3-butenoic acid 

X 

- 

- 

cis-2-Bromo-3-methylbutenedioic acid 

X 

- 

- 

Haloacetonitriles 

Dichloroacetonitrile 

X 

X 

X 

Bromochloroacetonitrile 

X 

X 

X 

Dibromoacetonitrile 

X 

X 

X 

Dibromochloroacetonitrile 

X 

- 

- 

Haloaldehydes 

2-Bromo-2-methylpropanal 

X 

X 

X 

Haloketones 

1,1 -Dichloropropanone 

X 

X 

_ 

1 -Bromo-1 -chloropropanone 

X 

X 

- 

1,1,1 -Trichloropropanone 

X 

- 

- 

1 -Bromo-1,1 -dichloropropanone 

X 

- 

- 

1,1,3-Tribromo-3-chloropropanone 

- 

- 

X 

1,1,3,3-Tetrabromopropanone 

- 

- 

X 

Pentachloropropanone 

X 

- 

X 

Hexachloropropanone 

X 

- 

- 

Halonitromethanes 

Dichloronitromethane 

X 

X 


Bromochloronitromethane 

X 

- 

- 

Bromodichloronitromethane 

X 

- 

- 

Halofuranones 

Ox-MX 

X 



Miscellaneous Halogenated DBPs 

1,2-Dichloroethylbenzene 

X 



Dichlorophenol 

- 

- 

X 

T etrachlorocyclopentadiene 

X 

- 

- 

Hexachlorocyclopentadiene 

X 

- 

- 

Bromopentachlorocyclopentadiene 

X 

- 

- 

Non-halogenated DBPs 

Glyoxal 

X 



4-Methylpentanoic acid 

- 

- 

X 

Dodecanoic acid 

X 

- 

- 


a DBPs detected by broadscreen gas chromatography/mass spectrometry (GC/MS) technique. 
b Compounds listed in italics were confirmed through the analysis of authentic standards; 
haloacids and non-halogenated carboxylic acids identified as their methyl esters. 


288 

























Table 16. DBP results at 


09/05/2001 

MRL a 

pg/L 

Aldrich 1 

Conventional 1 

Combined Plant 1 

Compound 

Raw 

Clearwell 

Raw 

Basins 4&5 

Basins 1&2 

Filt Eff 

Finished 

DS/Ave 

S DS/Ave 

SDS/Max 

Halomethanes 












Chloromethane 

0.2 

ND C 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Bromomethane 

0.2 

ND 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Bromochloromethane 

0.5 

ND 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Dibromomethane 

0.5 

ND 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Chloroform d 

0.1 

ND 

100 

0.2 

100 

120 

110 

120 

150 

120 

270 

Bromodichloromethane d 

0.1 

ND 

40 

ND 

40 

50 

40 

40 

50 

30 

60 

Dibromochloromethane d 

0.1 

ND 

4 

ND 

4 

4 

4 

4 

6 

4 

9 

Bromoform d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

0.2 

0.2 

THM4 f 

0 

ND 

144 

ND 

144 

174 

154 

164 

206 

154 

339 

Dichloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromoiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 

ND 

0.3 

ND 

ND 


ND 

ND 

ND 

ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 












Monochloroacetic acid d 

2 


9.0 


5.9 

6.5 

ND 

2.4 

5.2 

ND 


Monobromoacetic acid d 

1 


1.2 


1.1 

1.2 

ND 

ND 

1.0 

ND 


Dichloroacetic acid d 

1 


64 


51 

53 

13 

24 

41 

26 


Bromochloroacetic acid d 

1 


9.4 


9.0 

9.0 

2.4 

4.4 

6.1 

5.4 


Dibromoacetic acid d 

1 


ND 


1.0 

1.0 

ND 

ND 

ND 

ND 


Trichloroacetic acid d 

1 


91 


90 

85 

73 

80 

87 

82 


Bromodichloroacetic acid 

1 


19 


16 

18 

16 

17 

18 

18 


Dibromochloroacetic acid 

1 


1.2 


1.9 

1.1 

1.1 

1.7 

1.2 

1.8 


Tribromoacetic acid 

2 


3.3 


2.7 

2.5 

ND 

ND 

2.4 

ND 


HAA5 9 



165 


149 

147 

86 

106 

134 

108 


HAA9 h 



198 


179 

177 

106 

130 

162 

133 


DXAA' 



73 


61 

63 

15 

28 

47 

31 


TXAA 1 



115 


111 

107 

90 

99 

109 

102 


Haloacetonitriles 












Chloroacetonitrile 

0.1 

ND 

1 

ND 

0.6 

0.8 

0.6 

0.7 

0.9 

1 

0.9 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

0.2 

0.3 

Dichloroacetonitrile d 

0.1 

ND 

22 

ND 

21 

23 

9 

12 

19 

16 

18 

Bromochloroacetonitrile d 

0.1 

ND 

1 

ND 

2 

2 

0.6 

1 

2 

1 

1 

Dibromoacetonitrile d 

0.1 

ND 

0.2 

ND 

0.4 

ND 

ND 

ND 

0.3 

ND 

0.2 

T richloroacetonitrile d 

0.1 

ND 

ND 

ND 

0.2 

0.2 

0.1 

0.1 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 



ND 

0.8 


ND 

ND 




Dibromochloroacetonitrile 

0.5 



ND 

ND 


ND 

ND 




T ribromoacetonitrile 

0.91 



ND 

ND 


ND 

ND 




Haloketones 












Chloropropanone 

0.1 

ND 

0.5 

ND 

0.7 

0.7 

0.8 

0.8 

1 

0.7 

0.8 

1,1 -Dichloropropanone d 

0.10 

ND 

0.5 

ND 

0.6 

1 

0.9 

0.8 

0.4 

0.5 

0.2 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T richloropropanone d 

0.1 

ND 

7 

ND 

9 

8 

6 

7 

7 

7 

0.8 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

0.1 

ND 

ND 

ND 

0.3 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -Tribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NR 8 

NR 

1,1,3-T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrachloropropanone 

0.1 

ND 

0.2 

ND 

0.2 

1 

ND 

ND 

0.3 

0.3 

0.1 

1,1,1,3-T etrachloropropanone 

0.10 

ND 

0.3 

ND 

0.3 

0.8 

0.5 

0.4 

0.3 

0.4 

0.2 

1,1,3,3-Tetrabromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


289 









































































Table 16 (continued) 


09/05/2001 

MRL* 

pg/L 

Aldrich 1 

Conventional 1 

Combined Plant 

Compound 

Raw 

Clearwell 

Raw 

Basins 4&5 

Basins 1&2 

Filt Eff 

Finished 

DS/Ave 

SDS/Ave 

SDS/Max 

Haloacetaldehydes 












Dichloroacetaldehyde 

0.221 

ND 

4 

ND 

4 

7 

3 

4 

3 

4 

2 

Bromochloroacetaldehyde 

0.5 

ND 

2 

ND 

2 

2 

0.7 

ND 

ND 

1 

ND 

Chloral hydrate d 

0.1 

ND 

29 

2 

22 

22 

16 

16 

26 

28 

62 

Tribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 












Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

ND 

0.3 

ND 

0.4 

0.2 

ND 

ND 

0.2 

0.2 

0.3 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin d 

0.1 

ND 

2 

ND 

1 

0.8 

0.8 

0.7 

1 

0.7 

1 

Bromodichloronitromethane 

0.5 



ND 

0.9 


0.5 

0.6 




Dibromochloronitromethane 

0.505 



ND 

ND 


ND 

ND 




Bromopicrin 

2.1 



ND 

ND 


ND 

ND 




Miscellaneous Compounds 












Methyl ethyl ketone 

0.5 

ND 

ND 

ND 

0.6 


0.6 

0.6 

0.6 

0.7 


Methyl tertiary butyl ether 

0.2 

1.6 

1.0 

1.3 

1.0 


1.0 

0.9 

0.8 

1.0 


Benzyl chloride 

0.5 

ND 

ND 

ND 

ND 

NR 

ND 

ND 

ND 

ND 

NR 

1,1,2,2-Tetrabromo-2-chloroethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


290 






































Table 17. DBP results at plant 9 (8/27/01) 


08/27/2001 

"mr17 

Plant 9 k 

Compound 

pg/L 

Raw 

1 u Cond 

Basin #6 

Filt Inf 

Finished 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Halomethanes 











Chloromethane 

0.2 

ND C 

ND 

ND 


ND 

ND 


ND 


Bromomethane 

0.2 

ND 

ND 

ND 


ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 

ND 

ND 


ND 

ND 


ND 


Dibromomethane 

0.5 

ND 

ND 

ND 


ND 

ND 


ND 


Chloroform 1 * 

0.1 

ND 

4 

4 

5 

4 

6 

8 

5 

5 

Bromodichloromethane d 

0.1 

ND 

2 

2 

2 

2 

3 

2 

3 

2 

Dibromochloromethane d 

0.1 

ND 

0.3 

0.5 

0.9 

1 

1 

0.7 

1 

1 

Bromoform d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

THM4' 


ND 

6 

7 

8 

7 

10 

11 

9 

8 

Dichloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromoiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 

ND 

ND 

ND 


ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 











Monochloroacetic acid d 

2 


ND 

ND 


ND 

ND 


ND 


Monobromoacetic acid d 

1 


ND 

ND 


ND 

ND 


ND 


Dichloroacetic acid d 

1 


8.4 

11 


15 

18 


17 


Bromochloroacetic acid d 

1 


1.7 

1.6 


2.9 

3.5 


3.7 


Dibromoacetic acid d 

1 


ND 

ND 


1.1 

1.3 


ND 


Trichloroacetic acid d 

1 


1.3 

1.1 


1.3 

1.6 


1.2 


Bromodichloroacetic acid 

1 


ND 

ND 


1.0 

1.0 


ND 


Dibromochloroacetic acid 

1 


ND 

ND 


ND 

ND 


ND 


Tribromoacetic acid 

2 


ND 

ND 


ND 

ND 


ND 


HAA5 9 



9.7 

12 


17 

21 


18 


HAA9 h 



11 

14 


21 

25 


22 


DXAA' 



10 

13 


19 

23 


21 


TXAA 1 



1.3 

1.1 


2.3 

2.6 


1.2 


Haloacetonitriles 











Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.1 

ND 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloroacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromoacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

T richloroacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 

ND 



ND 




ND 

Dibromochloroacetonitrile 

0.5 

ND 

ND 



ND 




ND 

T ribromoacetonitrile 

0.91 

ND 

ND 



ND 




ND 

Haloketones 











Chloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

0.1 

ND 

1,1-Dichloropropanone 

0.10 

ND 

0.7 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1 -Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T richloropropanone d 

0.1 

ND 

0.3 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-Trichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrachloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-Tetrachloropropanone 

0.10 

ND 

ND 

0.5 

0.2 

0.2 

ND 

ND 

ND 

0.4 

1,1,3,3-Tetrabromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


291 










































































Table 17 (continued) 


08/27/2001 

MRL“ 

ug/L 

Plant 9 k 

Compound 

Raw 

rCond 

Basin #6 

Filt Inf 

Finished 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

HaloacetaldehYdes 











Dichloroacetaldehyde 

0.221 

ND 

1 

1 

0.6 

1 

0.9 

ND 

0.2 

0.9 

Bromochloroacetaldehyde 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

0.8 

Chloral hydrate 1 * 

0.1 

ND 

0.5 

0.5 

ND 

0.3 

0.2 

ND 

ND 

0.6 

Tribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Halonitromethanes 











Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloronitromethane 

0.5 

ND 

ND 



ND 




0.6 

Dibromochloronitromethane 

0.51 

ND 

ND 



0.6 




ND 

Bromopicrin 

2.1 

ND 

ND 



ND 




ND 

Miscellaneous Compounds 











Methyl ethyl ketone 

0.5 

ND 

ND 

ND 


1 

0.5 


0.5 


Methyl tertiary butyl ether 

0.2 

0.2 

ND 

ND 


ND 

ND 


ND 


Benzyl chloride 

0.5 

ND 

ND 

ND 

NR e 

ND 

ND 

NR 

ND 

NR 

1,1,2,2-Tetrabromo-2-chloroethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND ND 

ND 


292 





































Table 18. DBP results at plant 10 (11/26/01) 

4 A ADI a ..... I 


11/26/2001 

"mrl 7 

Aldrich 1 

Conventional 1 

Combined Plant 1 

Compound 

Mg/L 

Raw 

Clearwell 

Raw 

Basins 4&5 

Basins 1&2 

Filt Eff 

Finished 

DS/Ave 

SDS/Ave 

SDS/Max 

Halomethanes 












Chloromethane 

0.2 

ND C 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Bromomethane 

0.2 

ND 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Bromochloromethane 

0.5 

ND 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Dibromomethane 

0.5 

ND 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Chloroform d 

0.2 

ND 

13 

ND 

10 

NS m 

12 

12 

14 

12 

NA n 

Bromodichloromethane d 

0.1 

ND 

5 

ND 

4 

NS 

4 

4 

5 

5 

NA 

Dibromochloromethane d 

0.1 

ND 

0.6 

ND 

0.4 

NS 

0.4 

0.5 

0.6 

0.6 

NA 

Bromoform d 

0.11 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

THM4 f 

0 

ND 

19 

ND 

14 

NS 

16 

17 

20 

18 

NA 

Dichloroiodomethane 

0.5 

ND 

1 

ND 

1 

NS 

0.9 

1 

1 

1 

NA 

Bromochloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

Dibromoiodomethane 

0.52 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

Iodoform 

2 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

Carbon tetrachloride 

0.2 

ND 

0.3 

ND 

ND 


ND 

ND 

ND 

ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

Haloacetic acids 












Monochloroacetic acid d 

2 


ND 


2.8 

NS 

ND 

ND 

3.5 

ND 


Monobromoacetic acid d 

1 


1.2 


ND 

NS 

1.0 

ND 

1.3 

1.2 


Dichloroacetic acid d 

1 


16 


14 

NS 

6.2 

11 

13 

11 


Bromochloroacetic acid d 

1 


2.3 


2.0 

NS 

ND 

2.4 

2.2 

2.4 


Dibromoacetic acid d 

1 


ND 


ND 

NS 

ND 

ND 

ND 

ND 


Trichloroacetic acid d 

1 


6.5 


5.4 

NS 

4.4 

6.1 

6.0 

6.1 


Bromodichloroacetic acid 

1 


1.1 


ND 

NS 

ND 

1.0 

ND 

1.0 


Dibromochloroacetic acid 

1 


ND 


ND 

NS 

ND 

ND 

ND 

ND 


Tribromoacetic acid 

2 


ND 


ND 

NS 

ND 

ND 

ND 

ND 


HAA5 9 



24 


22 

NS 

12 

17 

24 

18 


HAA9 h 



27 


24 

NS 

12 

21 

26 

22 


DXAA' 



18 


16 

NS 

6.2 

13 

15 

13 


TXAA 1 



7.6 


5.4 

NS 

4.4 

7.1 

6.0 

7.1 


Haloacetonitriles 












Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

Dichloroacetonitrile d 

0.1 

ND 

2 

ND 

1 

NS 

0.7 

1 

2 

1 

NA 

Bromochloroacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

0.3 

0.2 

NA 

Dibromoacetonitrile d 

0.14 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

T richloroacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

Bromodichloroacetonitrile 

0.5 



ND 

ND 


ND 

ND 




Dibromochloroacetonitrile 

0.5 



ND 

ND 


ND 

ND 




T ribromoacetonitrile 

0.5 



ND 

ND 


ND 

ND 




Haloketones 












Chloropropanone 

0.1 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

1,1 -Dichloropropanone d 

0.10 

ND 

1 

ND 

1 

NS 

0.6 

0.8 

1 

0.8 

NA 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

1,1-Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

1,1,1 -T richloropropanone d 

0.1 

ND 

1 

ND 

1 

NS 

0.8 

0.9 

1 

0.9 

NA 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

1 -Bromo-1,1 -dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

1,1,1 -T ribromopropanone 

2.5 

NR 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

1,1,3-T ribromopropanone 

0.14 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

1,1,3,3-T etrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

1,1,1,3-Tetrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

1,1,3,3-T etrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 


293 











































































Table 18 (continued) 


11/26/2001 

MRL a 

pg/L 

Aldrich 1 

Conventional 1 

Combined Plant' 

Compound 

Raw 

Clearwell 

Raw 

Basins 4&5 

Basins 1&2 

Filt Eff 

Finished 

DS/Ave 

SDS/Ave 

SDS/Max 

Haloacetaldehydes 












Dichloroacetaldehyde 

1.1 

ND 

4 

ND 

2 

NS 

2 

2 

3 

2 

NA 

Bromochloroacetaldehyde 

0.5 

ND 

0.9 

ND 

0.6 

NS 

ND 

0.6 

1 

1 

NA 

Chloral hydrate^ 

0.1 

ND 

2 

ND 

1 

NS 

1 

1 

2 

1 

NA 

T ri bromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

Halonitromethanes 












Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

Dichloronitromethane 

0.1 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

0.1 

0.1 

NA 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

Chloropicrin d 

0.1 

ND 

0.8 

ND 

0.4 

NS 

0.5 

0.5 

0.7 

0.6 

NA 

Bromodichloronitromethane 

0.5 



ND 

ND 


ND 

ND 




Dibromochloronitromethane 

0.5 



ND 

ND 


ND 

ND 




Bromopicrin 

0.90 



ND 

ND 


ND 

ND 




Miscellaneous Compounds 












Methyl ethyl ketone 

0.5 

ND 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Methyl tertiary butyl ether 

0.2 

ND 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Benzyl chloride 

0.25 

NR 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 

1,1,2,2-Tetrabromo-2-chloroethane 

0.5 

ND 

ND 

ND 

ND 

NS 

ND 

ND 

ND 

ND 

NA 


m NS = Not sampled 
n NA = Not available 


294 







































Table 19. DBP results at plant 9 (11/26/01) 


11/26/2001 

MRL a 

Plant 9 11 

Compound 

mq/l 

Raw 

1 u Cond 

Basin #6 

Filt Inf 

Finished 

DS/Ave 

DS/Max 

SDS/Ave 

SDS/Max 

Halomethanes 











Chloromethane 

0.2 

ND C 

ND 

ND 


ND 

ND 


ND 


Bromomethane 

0.2 

ND 

ND 

ND 


ND 

0.2 


ND 


Bromochloromethane 

0.5 

ND 

ND 

ND 


ND 

ND 


ND 


Dibromomethane 

0.5 

ND 

ND 

ND 


ND 

ND 


ND 


Chloroform d 

0.2 

ND 

4 

2 

2 

3 

4 

6 

2 

NA n 

Bromodichloromethane d 

0.1 

ND 

2 

2 

2 

3 

5 

6 

2 

NA 

Dibromochloromethane d 

0.1 

ND 

0.9 

0.9 

2 

2 

4 

4 

2 

NA 

Bromofornr 

0.11 

ND 

ND 

0.1 

0.4 

0.4 

1 

1 

0.5 

NA 

THM4 f 


ND 

7 

5 

6 

8 

14 

17 

7 

NA 

Dichloroiodomethane 

0.5 

ND 

<0.5° 

<0.5 

NR e 

1 

2 

NR 

1 

NA 

Bromochloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

<0.5 

ND 

ND 

NA 

Dibromoiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

Bromodiiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

Iodoform 

2 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

Carbon tetrachloride 

0.2 

ND 

ND 

ND 


ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

Haloacetic acids 











Monochloroacetic acid d 

2 


ND 

ND 


ND 

2.4 


2.9 


Monobromoacetic acid d 

1 


1.2 

1.3 


1.2 

1.2 


ND 


Dichloroacetic acid d 

1 


5.1 

5.0 


6.2 

7.9 


6.2 


Bromochloroacetic acid d 

1 


1.8 

2.2 


2.5 

4.2 


3.4 


Dibromoacetic acid d 

1 


1.0 

1.3 


2.1 

3.0 


1.9 


Trichloroacetic acid d 

1 


ND 

ND 


ND 

ND 


ND 


Bromodichloroacetic acid 

1 


ND 

ND 


ND 

ND 


ND 


Dibromochloroacetic acid 

1 


ND 

ND 


ND 

ND 


ND 


Tribromoacetic acid 

2 


ND 

ND 


ND 

ND 


ND 


HAA5 9 



7.3 

7.6 


9.5 

15 


11 


HAA9 h 



9.1 

9.8 


12 

19 


14 


DXAA' 



7.9 

8.5 


11 

15 


12 


TXAA J 



ND 

ND 


ND 

ND 


ND 


Haloacetonitriles 











Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

NA 

Dichloroacetonitrile d 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

NA 

Bromochloroacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

Dibromoacetonitrile d 

0.14 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

T richloroacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

NA 

Bromodichloroacetonitrile 

0.5 

ND 

ND 



ND 




ND 

Dibromochloroacetonitrile 

0.5 

ND 

ND 



ND 




ND 

T ribromoacetonitrile 

0.5 

ND 

ND 



ND 




ND 

Haloketones 











Chloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

1,1 -Dichloropropanone 

0.10 

ND 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

NA 

1,1 -Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

NA 

1,1,1 -T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

NA 

1 -Bromo-1,1 -dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

1,1,1 -T ribromopropanone 

2.5 

ND 

ND 

ND 

NR 

ND 

ND 

NR 

ND 

NA 

1,1,3-T ribromopropanone 

0.14 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

NA 

1,1,3,3-Tetrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

NA 

1,1,1,3-Tetrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

NA 

1,1,3,3-Tetrabromopropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

NA 


295 









































































Table 19 (continued) 


11/26/2001 

MRL d 

mq/l 

Plant 9 k 

Compound 

Raw 

1 u Cond 

Basin #6 

Filt Inf 

Finished 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloacetald i eh^des 











Dichloroacetaldehyde 

1.1 

ND 

1 

2 

2 

2 

3 

2 

NA 

NA 

Bromochloroacetaldehyde 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

NA 

Chloral hydrate 6 

0.1 

ND 

0.3 

ND 

0.1 

ND 

0.6 

0.4 

NA 

NA 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

NA 

Halonitromethanes 











Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

NA 

Dichloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

0.2 

0.1 

ND 

NA 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 

Chloropicrin 6 

0.1 

ND 

ND 

ND 

ND 

ND 

0.3 

ND 

NA 

NA 

Bromodichloronitromethane 

0.5 

ND 

ND 



0.7 




0.7 

Dibromochloronitromethane 

0.5 

ND 

ND 



1 




ND 

Bromopicrin 

0.90 

ND 

ND 



2 




3 

Miscellaneous Compounds 











Methyl ethyl ketone 

0.5 

1 

ND 

ND 


ND 

0.8 


1 


Methyl tertiary butyl ether 

0.2 

ND 

ND 

ND 


ND 

ND 


ND 


Benzyl chloride 

0.25 

ND 

ND 

ND 

NR 

ND 

ND 

NR 

ND 

NA 

1,1,2,2-Tetrabromo-2-chloroethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

NA 


°<0.5 = Less than MRL (0.5 pg/L) 


296 



































Table 20. Additional target DBP results (ng/L) at Mississippi River WTPs (11/26/01) 

1 1 1 r>l— f nc ni * ina 


11/26/01 

Plant 9 C 

Plant 10 d 

Compound 

Soft. 

PC 

PE 

DS 

SDS 

Raw 

B4&5 

B1&2 

FE 

PE 

SDS 

Monochloroacetaldehyde 

0.0 

0.4 

0.0 


0.0 

0.0 

0.0 


0.0 

0.0 


Dichloroacetaldehyde 

0.0 

4.6 

5.0 


1.1 

0.0 

4.6 


2.5 

2.3 


Bromochloroacetaldehyde 

0.0 

0.2 

0.2 


0.0 

0.0 

0.6 


0.4 

0.80 


3,3-Dichloropropenoic acid 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.4 


0.4 

0.4 


Bromochloromethylacetate 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

NA 

0.0 

0.0 

0.0 

TOX (pg/L as Cl ) 

2.8 

82.7 

66.4 

99.2 


29.5 

207 


144 

175 


Cyanoformaldehyde 

<0.1 

<0.1 

<0.1 

NA 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

5-Keto-l-hexanal 

<0.1 

<0.1 

<0.1 

NA 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

6-Hydroxy-2-hexanone 

<0.1 

<0.1 

<0.1 

NA 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

Dimethylglyoxal 

0.3 

0.3 

0.2 

NA 

0.4 

<0.1 

0.7 

<0.1 

0.1 

0.3 

<0.1 

/ra/7.s-2-Hexenal 

<0.1 

<0.1 

<0.1 

NA 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 


c Plant 9 sampled at softened water rather than at raw water. 
d Plant 10 also sampled at SDS at maximum detection time. 


Table 21. Halogenated furanone results (jig/L) at Mississippi River WTPs (11/26/01) 


11/26/01 

Plant 9 C 

Plant 10 e 

Compound 

Soft. 

PC 

PE 

DS 

SDS 

Raw 

B4&5 

FE 

PE 

BMX-1 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

0.03 

<0.02 

<0.02 

BEMX-1 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

BMX-2 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

BEMX-2 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

BMX-3 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

0.02 

<0.02 

<0.02 

BEMX-3 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

<0.02 

MX 

<0.02 

<0.02 

<0.02 

(0.018) 

<0.02 

(0.013) 

NA 

<0.02 

0.40 

<0.02 

0.06 

EMX 

<0.02 

<0.02 

<0.02 

<0.02 

NA 

<0.02 

<0.02 

<0.02 

<0.02 

ZMX 

<0.02 

(0.01) 

0.03 

0.02 

<0.02 

NA 

<0.02 

<0.02 

0.04 

<0.02 

Ox-MX 

<0.02 

<0.02 

<0.02 

<0.02 

NA 

<0.02 

<0.02 

<0.02 

<0.02 

Mucochloric acid 

(ring) 

<0.02 

0.03 

0.08 

0.07 

NA 

<0.02 

<0.02 

0.03 

<0.02 

Mucochloric acid 
(open) 

<0.02 

(ooi) 

0.03 

0.08 

0.10 

NA 

<0.02 

<0.02 

0.03 

<0.02 


e Plant 10 sampled at (1) raw water, (2) B4&5, (3) FE, and (4) PE. 


297 


















































Table 22. DBP results at 


plant 10 (2/25/02) 


02/25/2002 

mrlT 

Aldrich 1 

Conventional' 

Combined Plant 1 

Compound 

mq/l 

Raw 

Clearwell 

Raw 

Basins 4&5 

Basins 1&2 

Filt Eff 

Finished 

DS/Ave 

S DS/Ave 

SDS/Max 

Halomethanes 












Chloromethane 

0.2 

ND C 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Bromomethane 

0.2 

ND 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Bromochloromethane 

0.5 

ND 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Dibromomethane 

0.5 

ND 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Chloroform d 

0.2 

ND 

8 

ND 

5 

NR e 

8 

10 

11 

11 

NR 

Bromodichloromethane d 

0.2 

ND 

3 

ND 

2 

NR 

3 

4 

5 

5 

4 

Dibromochloromethane d 

0.2 

ND 

0.5 

ND 

0.4 

NR 

0.4 

0.6 

0.7 

0.7 

0.7 

Bromoform d 

0.2 

ND 

<0.2 P 

ND 

<0.2 

ND 

<0.2 

<0.2 

<0.2 

<0.2 

ND 

THM4 f 


ND 

12 

ND 

8 

NR 

12 

15 

17 

17 

NR 

Dichloroiodomethane 

0.5 

ND 

<0.5 

ND 

ND 

NR 

<0.5 

<0.5 

<0.5 

<0.5 

NR 

Bromochloroiodomethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromoiodomethane 

0.5 

ND 

ND 

ND 

ND 

NR 

ND 

ND 

ND 

ND 

NR 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodiiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 

ND 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 












Monochloroacetic acid d 

2 


2.5 


2.9 

NR 

ND 

ND 

ND 

ND 


Monobromoacetic acid d 

1 


ND 


ND 

NR 

ND 

ND 

ND 

ND 


Dichloroacetic acid d 

1 


12 


13 

NR 

14 

14 

14 

12 


Bromochloroacetic acid d 

1 


2.2 


2.2 

NR 

2.7 

2.7 

2.7 

2.0 


Dibromoacetic acid d 

1 


ND 


ND 

NR 

ND 

ND 

ND 

ND 


Trichloroacetic acid d 

1 


6.2 


6.9 

NR 

11 

11 

11 

6.9 


Bromodichloroacetic acid 

1 


1.3 


1.4 

NR 

2.6 

2.6 

2.5 

1.4 


Dibromochloroacetic acid 

1 


3.0 


4.0 

NR 

2.9 

2.5 

2.7 

1.4 


Tribromoacetic acid 

2 


ND 


ND 

NR 

ND 

ND 

ND 

ND 


HAA5 9 



21 


23 

NR 

25 

25 

25 

19 


HAA9 h 



27 


30 

NR 

33 

33 

33 

24 


DXAA' 



14 


15 

NR 

17 

17 

17 

14 


TXAA 1 



11 


12 

NR 

17 

16 

16 

9.7 


Haloacetonitriles 












Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.2 

ND 

0.4 

ND 

0.5 

NR 

0.4 

0.5 

0.4 

0.4 

NR 

Bromochloroacetonitrile d 

0.2 

NR 

ND 

ND 

ND 

NR 

ND 

ND 

ND 

ND 

NR 

Dibromoacetonitrile d 

1.0 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

T richloroacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 



ND 

ND 


ND 

ND 




Dibromochloroacetonitrile 

0.5 



ND 

ND 


ND 

ND 




T ribromoacetonitrile 

0.955 



ND 

ND 


ND 

ND 




Haloketones 












Chloropropanone 

0.5 

ND 

ND 

ND 

ND 

NR 

ND 

ND 

ND 

ND 

NR 

1,1 -Dichloropropanone d 

1.0 

ND 

<1 q 

ND 

<1 

NR 

ND 

<1 

<1 

<1 

NR 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T richloropropanone d 

0.5 

NR 

0.9 

ND 

0.6 

NR 

0.5 

0.9 

1 

0.7 

NR 

1,1,3-T richloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

0.1 

ND 

ND 

ND 

<1 

ND 

1,1,1-Tribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-T etrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-T etrabromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


298 








































































Table 22 (continued) 


02/25/2002 

MRL 5 

mq/l 

Aldrich 1 

Conventional 1 

Combined Plant 1 

Compound 

Raw 

Clearwell 

Raw 

Basins 4&5 

Basins 1&2 

Filt Eff 

Finished 

DS/Ave 

SDS/Ave 

SDS/Max 

Haloacetaldehydes 












Dichloroacetaldehyde 

0.98 

ND 

2 

ND 

2 

3 

2 

2 

2 

4 

3 

Bromochloroacetaldehyde 

0.5 

ND 

0.5 

ND 

ND 

0.6 

ND 

ND 

0.7 

1 

0.9 

Chloral hydrate d 

0.1 

ND 

0.8 

0.2 

0.7 

2 

0.9 

1 

1 

2 

2 

T ribromoacetaldehyde 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

<1 

ND 

Halonitromethanes 












Chloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.10 

ND 

ND 

ND 

ND 

0.1 

ND 

ND 

ND 

ND 

0.1 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin d 

0.25 

ND 

0.5 

ND 

0.3 

ND 

0.5 

0.6 

0.7 

0.6 

NR 

Bromodichloronitromethane 

0.5 



ND 

0.5 


ND 

ND 




Dibromochloronitromethane 

0.5 



ND 

ND 


ND 

ND 




Bromopicrin 

0.5 



ND 

ND 


ND 

ND 




Miscellaneous Compounds 












Methyl ethyl ketone 

0.5 

2 

ND 

ND 

ND 


ND 

ND 

ND 

ND 


Methyl tertiary butyl ether 

0.2 

ND 

ND 

ND 

ND 


ND 

ND 

0.7 

1 


Benzyl chloride 

0.5 

ND 

ND 

ND 

ND 

NR 

ND 

ND 

ND 

ND 

NR 

1,1,2,2-Tetrabromo-2-chloroethane 

0.11 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


p <0.2 = Less than MRL (0.2 |jg/L) 
q <1 = Less than MRL (e.g., 1 |jg/L) 


299 








































Table 23. DBP results at plant 9 (2/25/02) 


02/25/2002 

■mrl7 

pg/L 

Plant 9 k 

Compound 

Raw 

1 u Cond 

Basin #6 

Filt Inf 

Finished 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Halomethanes 











Chloromethane 

0.2 

ND C 

ND 

ND 


ND 

ND 


ND 


Bromomethane 

0.2 

ND 

ND 

ND 


ND 

ND 


ND 


Bromochloromethane 

0.5 

ND 

ND 

ND 


ND 

ND 


ND 


Dibromomethane 

0.5 

ND 

ND 

ND 


ND 

ND 


ND 


Chloroform d 

0.2 

ND 

3 

1 

NR e 

2 

4 

NR 

2 

1 

Bromodichloromethane d 

0.2 

ND 

4 

2 

NR 

2 

3 

NR 

3 

2 

Dibromochloromethane d 

0.2 

ND 

2 

1 

NR 

2 

1 

NR 

2 

1 

Bromoform d 

0.2 

ND 

0.4 

<0.2 P 

- NR 

0.3 

0.3 

NR 

0.4 

0.2 

THM4' 


ND 

9 

4 

NR 

6 

8 

NR 

7 

4 

Dichloroiodomethane 

0.5 

ND 

<0.5° 

<0.5 

NR 

<0.5 

0.5 

NR 

<0.5 

ND 

Bromochloroiodomethane 

0.5 

ND 

<0.5 

<0.5 

ND 

<0.5 

<0.5 

ND 

<0.5 

ND 

Dibromoiodomethane 

0.5 

ND 

ND 

ND 

NR 

ND 

ND 

NR 

ND 

ND 

Chlorodiiodomethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

0.6 

ND 

ND 

Bromodiiodomethane 

0.52 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Iodoform 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Carbon tetrachloride 

0.2 

ND 

ND 

ND 


ND 

ND 


ND 


T ribromochloromethane 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Haloacetic acids 











Monochloroacetic acid d 

2 


ND 

ND 


ND 

ND 


ND 


Monobromoacetic acid d 

1 


ND 

ND 


ND 

ND 


ND 


Dichloroacetic acid d 

1 


6.2 

4.0 


4.9 

7.6 


4.5 


Bromochloroacetic acid d 

1 


3.7 

2.4 


3.0 

2.6 


3.4 


Dibromoacetic acid d 

1 


3.0 

2.2 


2.7 

2.2 


1.8 


Trichloroacetic acid d 

1 


1.1 

ND 


ND 

1.3 


ND 


Bromodichloroacetic acid 

1 


1.2 

ND 


ND 

ND 


ND 


Dibromochloroacetic acid 

1 


ND 

ND 


ND 

ND 


ND 


Tribromoacetic acid 

2 


ND 

ND 


ND 

ND 


ND 


HAA5 9 



10 

6.2 


7.6 

11 


6.3 


HAA9 h 



15 

8.6 


11 

14 


10 


DXAA' 



13 

8.6 


11 

12 


10 


TXAA 1 



2.3 

ND 


ND 

1.3 


ND 


Haloacetonitriles 











Chloroacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromoacetonitrile 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloroacetonitrile d 

0.2 

ND 

0.4 

ND 

NR 

0.2 

ND 

NR 

ND 

0.2 

Bromochloroacetonitrile d 

0.2 

ND 

0.8 

ND 

NR 

0.2 

ND 

NR 

ND 

0.4 

Dibromoacetonitrile d 

1.0 

ND 

<1 q 

<1 

<1 

<1 

ND 

<1 

<1 

<1 

T richloroacetonitrile d 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloroacetonitrile 

0.5 

ND 

ND 



ND 




ND 

Dibromochloroacetonitrile 

0.5 

ND 

ND 



ND 




ND 

T ribromoacetonitrile 

0.96 

ND 

ND 



ND 




ND 

Haloketones 











Chloropropanone 

0.5 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dichloropropanone d 

1.0 

ND 

<1 

ND 

NR 

ND 

ND 

NR 

ND 

ND 

1,3-Dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1-Dibromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -Trichloropropanone d 

0.5 

ND 

0.5 

ND 

NR 

ND 

ND 

NR 

ND 

ND 

1,1,3-Trichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1 -Bromo-1,1 -dichloropropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1 -T ribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3-Tribromopropanone 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,1,3-Tetrachloropropanone 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

1,1,3,3-Tetrabromopropanone 

0.1 

ND 

ND 

ND 

ND ND 

ND 

ND 

ND 

ND 


300 











































































Table 23 (continued) 


02/25/2002 

"mrl* 

mq/l 

Plant 9 k 

Compound 

Raw 

1 u Cond 

Basin #6 

Filt Inf 

Finished 

DS/Ave 

DS/Max 

S DS/Ave 

SDS/Max 

Haloacetaldehydes 











Dichloroacetaldehyde 

0.98 

ND 

1 

2 

2 

2 

2 

2 

2 

3 

Bromochloroacetaldehyde 

0.5 

ND 

ND 

ND 

ND 

ND 

<0.5 

ND 

ND 

0.5 

Chloral hydrate d 

0.1 

0.5 

0.4 

0.2 

0.3 

0.1 

0.5 

0.1 

0.2 

0.7 

T ribromoacetaldehyde 

0.1 

<1 

ND 

ND 

ND 

ND 

<1 

ND 

ND 

<1 

Halonitromethanes 











Chloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromonitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dichloronitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

0.1 

ND 

ND 

ND 

Bromochloronitromethane 

0.1 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Dibromonitromethane 

0.10 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Chloropicrin d 

0.25 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

Bromodichloronitromethane 

0.5 

ND 

0.6 



0.6 




0.9 

Dibromochloronitromethane 

0.5 

ND 

0.6 



0.6 




0.9 

Bromopicrin 

0.5 

ND 

ND 



ND 




ND 

Miscellaneous Compounds 











Methyl ethyl ketone 

0.5 

ND 

ND 

ND 


ND 

ND 


ND 


Methyl tertiary butyl ether 

0.2 

ND 

ND 

ND 


ND 

ND 


ND 


Benzyl chloride 

0.5 

ND 

ND 

ND 

NR 

ND 

ND 

NR 

ND 

ND 

1,1,2,2-Tetrabromo-2-chloroethane 

0.11 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 


301 





































Halo acids. At plant 10 in January and April 2001, chlorine and/or chloramine 
disinfection resulted in the formation of 83-95, 77-90, and 42-51 pg/L of the five regulated 
haloacetic acids (HAA5) in the Aldrich purification units, in basins 4 and 5, and in basins 1 and 
2, respectively. As with the THM results, less HAAs were produced in basins 1 and 2 in January 
and April 2001 because of the earlier addition of ammonia to form chloramines. Chlorine only 
disinfection in September 2001 resulted in the formation of 165, 149, and 147 pg/L of HAA5 in 
the Aldrich purification units, in basins 4 and 5, and in basins 1 and 2, respectively. In contrast, 
the use of chloramines only at plant 10 in November 2001 and February 2002 resulted in the 
formation of 21-24 pg/L of HAA5 in the Aldrich purification units and in basins 4 and 5. 

At plant 9 in January 2001, April 2001, August 2001, November 2001, and February 
2002, chlorine/chloramine disinfection resulted in the formation of 4-18 pg/L of HAA5. Higher 
formation of HAAs was observed in April and August as compared to in January 2001, with 
intermediate HAA formation in November 2001 and February 2002. 

In addition, all nine HAAs (HAA9) were measured, which included all of the brominated 
HAA species. At plant 10, the level of HAA9 in the Aldrich purification units, in basins 4 and 5, 
and in basins 1 and 2, was 104-114, 92-114, and 52-61 pg/L, respectively, in January and April 
2001 and was 177-198 pg/L in September 2001. In contrast, with chloramines only, HAA9 was 
24-30 pg/L in November 2001 and February 2002 in the Aldrich Purification units and in basins 
4 and 5. At plant 10, HAA formation was higher than THM formation. At plant 9, the level of 
HAA9 in the finished water was 6-21 pg/L. 

When pre-chlorination was used at plant 10 (January, April, and September 2001), 
trihalogenated HAAs (TXAAs) were in higher proportion than the dihalogenated species 
(DXAAs) (e.g., 111 versus 61 pg/L in basins 4&5 in September 2001). In other research, 

TXAAs were found to constitute the greatest mole fraction of HAA9 in chlorinated waters at pH 
8 (Cowman and Singer, 1996). (The plant 10 waters were chlorinated at pH levels in the range 
of 7 to 8.) When pre-chloramination was used at plant 10 (November 2001 and February 2002), 
DXAAs were in higher proportion than the TXAAs (e.g., 16 versus 5 pg/L in basins 4&5 in 
November 2001). In other research, chloramines have been shown to produce little or no THMs 
and TXAAs, whereas DXAAs formed (Krasner et al., 1996). With either pre-chlorination or pre- 
chloramination at plant 10, in each HAA subgroup (monohalogenated HAAs [MXAAs], 

DXAAs, TXAAs), the fully chlorinated species (monochloro-, dichloro-, and trichloroacetic 
acid) predominated, followed by the bromochloro species (bromochloro- and 
bromodichloroacetic acid) (Figure 4). 

At plant 9, most of the HAAs that were formed were DXAAs; very low amounts of 
TXAAs were detected (Figure 5). In other research, pH (in the range of 5 to 9.4) had no 
significant effect on dichloroacetic acid formation, whereas trichloroacetic acid formation was 
lower at pH 9.4 than at the lower pH levels (and THM formation was higher with increasing pH) 
(Stevens et ah, 1989). The THM and HAA (DXAA versus TXAA) data (Figure 5) suggest the 
following: (1) minimal free chlorine contact time and the very high pH of chlorination (typically 
~10) initially impacted the DBP formation and speciation; and (2) the presence of chloramines in 


302 


Figure 4. HAA speciation in Basins 4&5 at plant 10 in September 2001 



the downstream basins minimized further THM and TXAA formation but allowed DXAAs to 
continue to form. 

In other research, it was demonstrated that HAAs can be removed by GAC filtration, 
presumably by biodegradation processes within the filter bed (Singer et al., 1999). The extent of 
removal depended upon water temperature and the residual chlorine concentration. Because the 
combined filter effluent at the conventional plant was a combination of water from basins 4&5 
and basins 1&2, the filter effluent was compared to a flow-weighted filter influent. For example, 
in April 2001, basins 4&5 had a flow of 20.6 mgd and 43 pg/L of DXAAs, and basins 1&2 had a 
flow of 11 mgd and 27 pg/L of DXAAs. So the flow-weighted filter influent had 37 pg/L of 
DXAAs: (20.6 x 43 + 11 x 27)/(20.6 + 11). Figure 6 shows the seasonal variations in HAA 
removal through the GAC filters. In January 2001, HAAs were not removed when the water 
temperature was 0.3-3.5°C. In April 2001, when the water temperature was 14-15°C, the 
DXAAs were reduced in concentration by 35 %, whereas the levels of the other two subclasses 
of HAAs were relatively constant. In September 2001, when the water temperature was 27- 
29°C, the DXAAs were reduced in concentration by 75 % and the MXAAs were not detected 
(ND) in the filter effluent, whereas the level of TXAAs was marginally reduced. In November 
2001, when the water temperature was 13-16°C, the DXAAs and MXAAs were reduced in 
concentration by 61 and 64 %, respectively, whereas the level of TXAAs was marginally 
reduced. In February 2002, HAA data were not available for basins 1&2. Because most of the 


303 




Figure 5. Impact of chloramines and pH of chlorination (~10) on THM and 
HAA formation and speciation at plant 9: August 27, 2001 



flow in the conventional treatment train was from basins 4&5, the data for the former basins 
were used to estimate the combined filter influent concentrations. In the latter month, when the 
water temperature was 6°C, the DXAAs and TXAAs were not removed, and the MXAAs were 
not detected (ND) in the filter effluent. These results are consistent with other research in which 
DXAAs were found to be biodegradable, whereas TXAAs were not, and the phenomenon was 
temperature dependent (Baribeau et al., 2000). 


304 
























Figure 6. Seasonal variations in removal of HAAs through GAC filters at plant 10: water 
temperature at filters provided by each sample date (ND = not detected in filter effluent) 


c 

o 

3 


<D 


■o 

0) 


O) 

‘3 

$ 

l 

£ 

o 


♦3 

c 

Q 

ifc 

III 

k. 

O 



120 % 

100 % 

80% 

60% 

40% 

20 % 

0% 

TXAAs 


DXAAs 


01/10/2001 (0.3-3.5 C) 
04/09/2001 (14-15 C) 
09/05/2001 (27-29 C) 
11/26/2001 (13-16 C) 
02/25/2002 (6 C) 


MXAAs 


Figure 7 shows a comparison of DXAA and TXAA speciation at the two Mississippi 
River WTPs. The use of either chloramines or disinfection at pH levels of >9 favored DXAA 
formation over TXAA formation at plant 9, whereas pre-chlorination at pH 7-8 at plant 10 
(January, April, and summer 2001) resulted in somewhat more TXAA formation than DXAA 
formation. Alternatively, pre-chloramination at pH 7-8 at plant 10 (November 2001 and 
February 2002) resulted in somewhat more DXAA formation than TXAA formation. Also, 
GAC filtration (in the conventional treatment trains) at plant 10 was more effective at removing 
DXAAs than TXAAs (especially in summer 2001). Thus, the difference in HAA speciation at 
these two utilities reflected the different effects of chlorine and chloramines, as well as pH and 
GAC filtration, on HAA formation and control. 


305 





























Figure 7. Impact of chloramines and chlorine, pH and GAC filtration 
on HAA speciation at plant 9 and plant 10 


o 


I 

U) 



Plant 9 
Primary 
Conditioner 


Plant 9 
Finished 
Water 


2/25/2002 
11/26/2001 
Summer 2001 
4/9/2001 
1 / 10/2001 


Plant 10 
Aldrich Plant 10 
Purification C° nv - Train 

Units Filter 

Effluent 


In addition to the target HAAs, two other haloacids were detected at plant 10 in April 
2001 by the broadscreen GC/MS methods: 3,4,4-trichloro-3-butenoic acid and cw-2-bromo-3- 
methylbutenedioic acid (Table 15). November 2001 results from UNC also show the presence of 
another target halo-acid, 3,3-dichloropropenoic acid, at a level of 0.4 pg/L in finished waters 
from plant 10 (Table 20). 

Haloacetonitriles. In other research, haloacetonitriles (HANs) have been found to be 
produced at approximately one-tenth the level of the THMs (Oliver, 1983). In the plant 10 
samples, a comparison was made between the four HANs in the Information Collection Rule 
(ICR) (HAN4) (dichloro- [DCAN], bromochloro-, dibromo-, and trichloroacetonitrile [TCAN]) 
and THM4. The ratio of HAN4 to THM4 (on a weight basis) for the January, April, and 
September 2001 samplings was 8, 15, and 16 %, respectively. 

A similar relationship was also observed (in part) in the plant 9 samples. Because the 
THM concentrations were at low pg/L levels at plant 9, the ICR HANs were detected at sub- 
pg/L levels. The major HAN formed, DCAN, typically went down in concentration in the plant, 
distribution system, and/or SDS samples. DCAN undergoes base-catalyzed hydrolysis (Croue 
and Reckhow, 1989), so it is not surprising that it would not be stable at the pH of treatment and 
distribution at plant 9 (i.e., pH = 9-10). 


306 

























































Similar to the HAAs (Figure 6), seasonal variations in the removal of DCAN through 
GAC filters was evaluated (Figure 8). In January 2001 and February 2002, the concentration of 
DCAN was 74-80 % of the level in the flow-weighted filter influent. In April and November 
2001, when the water temperature was warmer, DCAN was reduced in concentration by 30-47 
%. In September 2001, when the water temperature was the warmest, DCAN was reduced in 
concentration by 58 %. These results are similar to the seasonal removal of DXAAs (Figure 6). 

Figure 8. Seasonal variations in removal of other DBPs through GAC filters at plant 10: 
water temperature at filters provided by each sample date (results arranged in order of 
decreasing water temperature); N/A = not available 


<D 


•u 

0) 


O) 

'3 

I 


5 

c 

<u 

3 

8 = 

HI 

l- 

o 



120 % 


100 % 


80% 


= 60% 


40% 


20 % 


01/10/2001 (0.3-3.5 C) 
02/25/2002 (6 C) 
11/26/2001 (13-16 C) 
04/09/2001 (14-15 C) 
09/05/2001 (27-29 C) 


A comparison of HAN formation was made between the primary conditioner at plant 9 
(at the beginning of the treatment process, prior to downstream base-catalyzed hydrolysis) and 
the effluent of basins 4&5 at plant 10 (before GAC filtration) for January, April, and November 
2001 (Figure 9). The ratio of HAN4 and THM4 (on a weight basis) was 6-10 % at plant 9 and 8- 
16 % at plant 10. The ratio was somewhat higher at plant 10, probably because of the lower pH 
of chlorination, which minimized base-catalyzed hydrolyis of the HANs. 

In addition to the ICR HANs, other target HANs (chloro-, bromo-, bromodichloro-, and 
dibromochloroacetonitrile) were detected in selected samples at plant 10. (The latter HAN was 
detected during the broadscreen GC/MS analyses [Table 15]). None of the other target HANs 
were detected at plant 9. 


307 












Figure 9. Relative formation of HANs to THMs at the Mississippi River WTPs 



1 / 10/2001 


Plant 10 Basins 4&5 


Plant 9 Primary Conditioner 


4/9/2001 


Summer 2001 


Haloketones. In addition to the formation of low levels of haloketone (HK) compounds 
from the ICR (1,1-dichloro- and 1,1,1-trichloropropanone), low levels of some of the target HKs 
were detected in some of the samples at plant 9 and plant 10 (Figure 10). At plant 10, the 
formation of 1,1,1-trichloropropanone was much higher, especially when pre-chlorination was 
utilized (e.g., April 2001). In other research, 1,1,1-trichloropropanone was detected at acidic and 
neutral pH levels, but was not detected at a pH of 9.4 (Stevens et al., 1989). Thus, the presence 
of chlorine for longer contact times at a lower pH level resulted in more formation of this HK at 
plant 10. Alternatively, 1,1-dichloropropanone levels were comparable at both plants in April 
2001, suggesting that pH did not impact this HK to the same extent. When pre-chlorination was 
used at plant 10, the level of 1,1,1-trichloropropanone was much higher than that of 1,1- 
dichloropropanone, whereas when pre-chloramination was used the levels of the two HKs were 
similar (Figure 10). 

Figure 11 shows the impact of distribution-system disinfectant on the formation and 
stability of THMs and HKs at plant 10, comparing the SDS samples set up for a maximum 
detention time (five days) to the original finished water. In April 2001, when chloramines were 
used, the concentrations of the THMs and many of the HKs were relatively constant. However, 
there was a significant increase in the formation of 1,1-dichloropropanone. In other research, 
chloramines were found to control the formation of THMs and TXAAs better than they control 
the formation of DXAAs (Krasner et al., 1996). Thus, 1,1-dichloropropanone may continue to 
form in chloraminated water. In September 2001, when chlorine was used, the concentration of 


308 



















Figure 10. Haloketone formation in finished waters at plant 9 (4/9/01) and plant 10 (4/9/01 
and 11/26/01) (haloketones not detected in finished water at plant 9 on 11/26/01) 



Figure 11. Plant 10 (N/A = not available): 


Impact of Distribution-System Disinfectant on the Formation and 
Stability of THMs and Haloketones in SDS/Maximum Detention Time 
Samples: Chloramines on 4/9/01, Chlorine on 9/5/01 


E 

3 

E 


x 


o 

*■« 

(0 

T3 

a> 


if) 

Q 

if) 


</> 

c 

il 



04/09/01 
09/05/01 


309 


















the THMs significantly increased, the concentration of chloropropanone was unchanged, and the 
concentrations of some of the other HKs decreased to varying degrees, especially that of 1,1,1- 
trichloropropanone (from 7 to 0.8 pg/L). In other research, 1,1,1- 

trichloropropanone was shown to decrease in the presence of chlorine, perhaps as a result of the 
direct reaction of chlorine with this HK (Reckhow and Singer, 1985). 

In addition to the target HKs, other HKs were detected in selected samples by the 
broadscreen GC/MS methods (Table 15). Two of these HKs were analogous to the di- and 
tetrahalogenated HKs monitored for by MWDSC, except that these were mixed bromochloro 
species. Another two HKs that were detected at these WTPs by the broadscreen GC/MS 
methods was pentachloro- (PCP) and hexachloropropanone (HCP). MWDSC had attempted to 
include PCP and HCP in its target compound list, but they both degraded immediately and 
completely in water under all conditions evaluated (Gonzalez et al., 2000). 

Haloaldehydes. In addition to the formation of chloral hydrate (trichloroacetaldehyde) 
(an ICR DBP), low levels of the target haloacetaldehydes (e.g., dichloroacetaldehyde) were 
detected at plant 10 (Figure 12). In January 2001, April 2001, and February 2002, chloraminated 
water was in settling basins 1 &2 (with upstream pre-chlorination in mixing tank number 2) 
(Figure 1), whereas in September 2001, chlorine only was in settling basins 1&2. The sum of the 
concentration of the two dihalogenated acetaldehydes (2.4-3.6 pg/L) was greater than the sum of 
the concentration of the two trihalogenated acetaldehydes (0.2-2 pg/L) when the water was 
chloraminated. When the water was chlorinated, chloral hydrate formation (22 pg/L) was much 
greater than the formation of the sum of the two dihalogenated acetaldehydes (9 pg/L). In 
addition, the warmer water temperature in September 2001 contributed to more haloacetaldehyde 
formation overall. 

In February 2002, pre-chloramination in basins 4&5 versus chlorine/chloramines in 
basins 1&2 resulted in much more control of chloral hydrate (0.7 versus 2 pg/L) than for 
dichloroacetaldehyde (2 versus 3 pg/L). In other research, chloramines were found to minimize 
the formation of chloral hydrate, whereas certain dihalogenated DBPs were formed to greater 
extents (Young et al., 1995). Consistent with that research, the formation of dihalogenated 
acetaldehydes was favored over trihalogenated species at plant 10 when chloramines were used, 
especially with pre-chloramination. 


310 


Figure 12. Haloacetaldehyde formation and speciation in Basins 1&2 at plant 10: 
chlorine/chloramines in January 2001, April 2001, and February 2002; chlorine only in 
September 2001 (Basins 4&5 with pre-chloramination in February 2002 provided for 
comparison) 



2/25/02: Basins 4&5 
2/25/02: Basins 1&2 
09/05/2001 
04/09/2001 
01 / 10/2001 


At plant 9, dichloroacetaldehyde formation was typically greater than that of chloral 
hydrate (Figure 13). This was due, in part, because chloral hydrate undergoes base-catalyzed 
hydrolysis at high pH (e.g., ~9) (Stevens et al., 1989). With the measurement of dihalogenated 
and/or brominated analogues of chloral hydrate, the haloacetaldehydes represented the third 
largest class of DBPs formed at plant 9 (on a weight basis). 


311 













































Figure 13. Seasonal variations in the formation and speciation of the haloacetaldehydes 
in the finished water of plant 9 



02/25/2002 
11/26/2001 
08/27/2001 
04/09/2001 
01 / 10/2001 


Figure 14 shows the relative speciation of the sum of the two measured dihalo- 
acetaldehydes (DXAs) to the sum of the four measured species. At plant 9, DXAs represented 
55 to 100 % (median = 89 %) of the measured haloacetaldehydes (HAs). At plant 10, the DXAs 
represented 64 to 92 % of the haloacetaldehydes in basins 1 &2 when chloramines were used and 
29 % of this class of DBPs when chlorine only was used. In February 2002, when pre- 
chloramination was used in basins 4&5, the DXAs represented 74 % of the haloacetaldehydes 
(Figure 12). 

As with the other classes of DBPs, the formation of the chlorinated species at plant 10 
was highest for each subclass of haloacetaldehyde, and the bromochloro species was next highest 
in concentration (Figure 12). 


312 


















Figure 14. Impact of chloramines and chlorine, and pH on haloacetaldehyde (HA) 
speciation (e.g., dihaloacetaldehydes [DXAs]) at the Mississippi River WTPs (NS = not 
sampled) 


</> 

< 

X 

1/5 

< 

X 

o 



2/25/2002 


Similar to the HAAs (Figure 6) and DC AN (Figure 8), seasonal variations in the removal 
of dichloro- and trichloroacetaldehyde [chloral hydrate]) were examined (Figure 8). In January 
2001 and February 2002, the concentrations of these two haloacetaldehydes were 84-119 % of 
the levels in the flow-weighted filter influents. In April 2001, when the water temperature was 
warmer, dichloroacetaldehyde was reduced in concentration by 37 % (data were not available 
(N/A) for chloral hydrate). However, in November 2001, when the water temperature was 
similar to that in April 2001, there was no reduction in the concentration of the 
haloacetaldehydes though the GAC filters. In September 2001, when the water temperature was 
the warmest, dichloroacetaldehyde and chloral hydrate were reduced in concentration by 39 and 
27 %, respectively. These results are similar, in part, to the relative seasonal removal of DXAAs 
and TXAAs (Figure 6) and DCAN (Figure 8). 

In addition to the target haloaldehydes, one other haloaldehyde was detected at both 
WTPs by the broadscreen GC/MS methods: 2-bromo-2-methylpropanal (Table 15). 

Halonitromethanes. Low levels of chloropicrin (trichloronitromethane) (an ICR DBP) 
were detected at plant 10. This DBP was only detected in the April and November 2001 samples 
at plant 9. Other halonitromethanes (HNMs) were detected in selected samples from both WTPs 


313 


























Figure 15. Halonitromethane formation at the Mississippi River WTPs in 
August/September 2001 



(e.g., Figure 15). Although there was a large difference in THM and HAA formation between 
the two utilities, the difference in HNM formation was not as high. 

As with the HAAs, there are nine HAN species and nine NHMs (two monohalogenated 
species, three dihalogenated species, and four trihalogenated species). The relative speciation of 
brominated and chlorinated HANs and HNMs (for the di- and trihalogenated species) was 
compared to the HAAs for the effluent of basins 4&5 from the September 2001 sampling. Each 
DBP can be abbreviated based on the number of halogens and the speciation of the halogens as 
follows: RBr y Cl z , where the number of bromine and chlorine atoms are y and z, respectively, 
and R corresponds to the remainder of the DBP molecule (i.e., carbon, hydrogen, oxygen, and 
nitrogen atoms). The concentration of each DBP was “normalized” by dividing its concentration 
by the sum of the concentrations of all of the DBPs for that “subclass” of DBPs (RX y+z ) 

(Figure 16). For example, the concentration of dichloroacetic acid was divided by the sum of all 
the DXAAs. 

For the dihalogenated DBPs (RX 2 ), the dichlorinated species represented 84 to 100 % of 
the sum of the dihalogenated DBPs in each class of DBPs examined. The bromochloro species 
represented 0 to 15 % of the class sums, and the dibromo species represented 0 to 2 % of the 
class sums. For the HAAs, HANs, and HNMs, there was a similar relative speciation of 
brominated and chlorinated DBPs for the dihalogenated subclass. For the trihalogenated DBPs 
(RX 3 ), the trichlorinated, bromodichlorinated, dibromochlorinated, and tribrominated species 


314 


























Figure 16. Effluent of Basins 4&5 at plant 10: 


Relative Speciation of Chlorinated and Brominated Species: 
Haloacetic Acids (HAAs), Haloacetonitriles (HANs), 
Halonitromethanes (HNMs): September 5, 2001 


K 

P I 

O 

CO 

UL 


represented 20 to 81 %, 14 to 80 %, 0 to 2 %, and 0 to 2 % of the subclass sums, respectively. 
Although not shown in this figure, for THM4, chloroform, bromodichloromethane, 
dibromochloromethane, and bromoform represented 69, 28, 3, and 0 % of that class sum, 
respectively. The relative speciation of the THMs was in between that of the speciation for the 
HAAs and the HNMs. The reason the relative speciation for the trihalogenated HANs may have 
been different is probably due to the relative instability of TCAN. In other research, TCAN has 
been shown to undergo base-catalyzed hydrolysis in the pH range of 7 to 8, whereas it is stable at 
pH 6 (Croue and Reckhow, 1989). The pH of basins 4&5 was 7.2, so it is likely that TCAN 
simultaneously formed and degraded in these basins. 

For plant 9, the relative speciation of brominated and chlorinated HNMs (for the 
trihalogenated species) was compared to the THMs, the dihaloacetonitriles (DHANs), and the 
DXAAs for the February 2002 finished water (Figure 17). (TXAAs and dihalogenated HNMs 
were not detected in this sample.) For the RX 2 , the dichlorinated species represented 33 to 46 % 
of the sum of the dihalogenated DBPs in that subclass of DBPs (on a weight basis). The 
bromochloro species represented 28 to 33 % of the subclass sum, and the dibromo species 
represented 25 to 33 % of the subclass sum. For the RX 3 , the trichlorinated, bromodichlorinated, 
dibromochlorinated, and tribrominated species for the HNMs and THMs represented 0 to 32 %, 
32 to 50 %, 32 to 50 %, and 0 to 5 % of the class sum, respectively. In February 2002, the raw- 
water bromide level was the highest for the plant 9 samples. For the THMs, HAAs, DHANs, 
and HNMs, there was a similar relative speciation of brominated and chlorinated DBPs at plant 
9, with a shift to more of the brominated species. 



315 



















Figure 17. Relative speciation of chlorinated and brominated species in finished water 
at plant 9 (2/25/02): dihaloacetic acids (DXAAs), dihaloacetonitriles (DHANs), 
trihalomethanes (THMs), trihalogenated halonitromethanes (tri-HNMs) 



Halogenatedfurcmones. Table 21 shows the results for halogenated fiiranones in the 
November 2001 sampling for plant 9 and plant 10. Data are included for 3-chloro-4- 
(dichloromethyl)-5-hydroxy-2[5H]-furanone, otherwise known as MX; (E)-2-chloro-3- 
(dichloromethyl)-4-oxobutenoic acid, otherwise known as EMX; (Z)-2-chloro-3- 
(dichloromethyl)-4-oxobutenoic acid (ZMX); the oxidized form of MX (Ox-MX); brominated 
forms of MX and EMX (BMXs and BEMXs); and mucochloric acid (MCA), which can be found 
as a closed ring or in an open form. Results are displayed graphically in Figure 17. 

There was an increase in the concentrations of MC A-ring and MCA -open in the presence 
of chloramines at plant 9 (11/26/01) (Table 21). Brominated analogues of MX were not detected 
at plant 9. Plant 10 showed a significant formation of MX, with a levels of 400 ng/L observed 
after treatment with chloramines (in a sample collected from settling basins 4 & 5) (Figure 18). 
However, subsequent GAC filtration removed the MX, with no MX measured in the filter 
effluent. This is consistent with the removal of other DBPs in this study during the filtration 
process, which was probably due to biodegradation and not adsorption. Following the addition 
of chloramines after GAC filtration, MX was reformed at a significantly lower level in the plant 
effluent (60 ng/L). Two brominated analogues of MX (BMX-1 and BMX-3) were also formed at 


316 









































Figure 18. Halogenated furanones. 


Plant 9 and Plant 10 (11/26/01) 


□ BMX-1 ■ BMX-2 ■ BMX-3 ■ MX 11EMX E3ZMX 

□ MCA (ring) DMCA (open) BBEMX-1 El BEMX-2 DBEMX-3 □ Ox-MX 


0.50 

0.45 

0.40 

0.35 

0.30 

0.25 

0.20 

0.15 

0.10 

0.05 

0.00 






1 

j 

| 








































































•tc-C; 


























mm 

H 






each analyte: 
ND or NA 




i 1 


Softened 

Prim. Cond. 

CI2+NH3 

PE 

DS/ave 

Filter+CI2+NH3 

SDS/max 

Raw 

Basins 4&5 

CI2+NH3 

comb FE 

GAC 

conv PE 

CI2+NH3 


CD 

2 . 


C 

Q) 

O 

c 

o 

o 

0) 

c 

o 

c 

(TJ 


TJ 

"po 

C 

o 

O) 

o 

CO 


Plant 9 


Plant 10 


Sampling Point 


plant 10 (30 and 20 ng/L, respectively), but GAC filtration was effective in removing them 
completely, and they were not reformed in the plant effluent samples (Table 21). In samples 
collected in April 2001 from plant 10, ox-MX was qualitatively identified in the plant effluent 
using broadscreen GC/MS analysis (Table 15). 

Volatile Organic Compounds (VOCs). Carbon tetrachloride, which is a VOC and a 
possible DBP, was detected (0.07-0.3 pg/L) in several samples at plant 10, but was not found in 
the raw water (MRL = 0.06 or 0.2 pg/L). As mentioned in a previous chapter, carbon 
tetrachloride has been detected by some utilities in gaseous chlorine cylinders (EE&T, 2000), 
due to imperfections in the manufacturing process or improper cleaning procedures. 

Methyl tertiary butyl ether (MtBE) was detected in the raw water of plant 10 on 
September 5, 2001 at a concentration of 1.6 pg/L. The level of MtBE decreased somewhat 
through plant 10. MtBE was detected (0.7-1 pg/L) in the distribution system and in SDS testing 
for plant 10 on February 25, 2002, but was not detected (with an MRL of 0.2 pg/L) in the raw 
water. MtBE was detected (0.2-0.3 pg/L) in the raw water samples for plant 9 in January and 
August 2001, but was not detected in the WTP samples (with an MRL of 0.2 pg/L). MtBE is a 
gasoline additive. 

Methyl ethyl ketone (MEK) was detected in plant 9 on August 27, 2001 at 0.5-1 pg/L, 
but was not detected at or above the MRL of 0.5 pg/L in the raw water. MEK was detected (1 
pg/L) in the raw water for plant 9 on November 26, 2001, and was detected in some downstream 
samples at 0.8-1 pg/L. MEK was detected in the plant 10 conventional treatment train at 0.6 


317 































































pg/L on September 5, 2001, but was not detected at or above the MRL of 0.5 pg/L in the raw 
water. MEK was detected (2 pg/L) in the raw water for the Aldrich purification units at plant 10 
on February 25, 2002, but was not detected in the treated water. MEK is an industrial solvent 
and it may also be a DBP. Because the level in the two WTPs in the summer 2001 samples was 
barely above the MRL, it can not be determined for sure if its presence was due to low-level raw- 
water contamination (as was observed in November 2001 at plant 9 and in February 2002 at 
plant 10 ) or if it was produced during the disinfection process. 

Other HalogenatedDBPs. A few additional, miscellaneous halogenated DBPs were also 
detected. UNC methods detected dichloroacetamide at 1.7 pg/L in finished water from plant 10 
(1/10/01) (Table 12). In addition, broadscreen GC/MS analyses revealed the presence of 1,2- 
dichloroethylbenzene, tetrachlorocyclopentadiene, hexachlorocyclopentadiene, and 
bromopentachlorocyclopentadiene in finished water collected from plant 10 in April 2001 (Table 
15). Dichlorophenol was identifed in finished water from plant 9 (Table 15). These compounds 
were not observed in the corresponding raw, untreated water. 

Non-Halogenated DBPs. Very few non-halogenated DBPs were detected in finished 
waters from plant 10 or plant 9. Dimethylglyoxal was identified at 0.2 and 0.3 pg/L in finished 
waters from plant 9 and plant 10, respectively, in November 2001 (Table 20). Broadscreen 
GC/MS analysis revealed the presence of glyoxal and dodecanoic acid in finished water from 
plant 10 (April 2001), and 4-methylpentanoic acid was found in finished waters from plant 9 
(August 2001) (Table 15). 


REFERENCES 

American Public Health Association (APHA). Standard Methods for the Examination of Water 
and Wastewater, 20th ed. APHA, American Water Works Association, and Water Environment 
Federation: Washington, DC (1998). 

Baribeau, H., S. W. Krasner, R. Chinn, and P. C. Singer. Impact of biomass on the stability of 
haloacetic acids and trihalomethanes in a simulated distribution system. Proceedings of the 
American Water Works Association Water Quality Technology Conference, American Water 
Works Association: Denver, CO, 2000. 

Cowman, G. A., and P. C. Singer. Effect of bromide ion on haloacetic acid speciation resulting 
from chlorination and chloramination of aquatic humic substances. Environmental Science & 
Technology 30( 1): 16 (1996). 

Croue, J.-P., and D. A. Reckhow. Destruction of chlorination byproducts with sulfite. 
Environmental Science & Technology 23(11): 1412 (1989). 

Environmental Engineering & Technology, Inc. (EE&T). Occurrence of, and Problems 
Associated With, Trace Contaminants in Water Treatment Chemicals. Progress report to 
AWWA Research Foundation, Denver, CO, 2000. 


318 


Gonzalez, A. C., S. W. Krasner, H. Weinberg, and S. D. Richardson. Determination of newly 
identified disinfection by-products in drinking water. Proceedings of the American Water Works 
Association Water Quality Technology Conference, American Water Works Association: 

Denver, CO, 2000. 

Krasner, S. W., J. M. Symons, G. E. Speitel, Jr., A. C. Diehl, C. J. Hwang, R. Xia, and S. E. 
Barrett. Effects of water quality parameters on DBP formation during chloramination. 
Proceedings of the American Water Works Association Annual Conference, Vol. D, American 
Water Works Association: Denver, CO, 1996. 

Oliver, B. G. Dihaloacetonitriles in drinking water: algae and fulvic acid as precursors. 
Environmental Science & Technology 17(2):80 (1983). 

Reckhow, D. A., and P. C. Singer. Mechanisms of organic halide formation during fulvic acid 
chlorination and implications with respect to preozonation. In Water Chlorination: Chemistry, 
Environmental Impact and Health Effects, Vol. 5 (R.L. Jolley et al., eds.); Lewis Publishers, Inc: 
Chelsea, MI, 1985. 

Singer, P. C., H. Arora, E. Dundore, K. Brophy, and H. S. Weinberg. Control of haloacetic acid 
concentrations by biofiltration: a case study. Proceedings of the American Water Works 
Association Water Quality Technology Conference, American Water Works Association: 

Denver, CO, 1999. 

Stevens, A. A., L. A. Moore, and R. J. Miltner. Formation and control of non-trihalomethane 
disinfection by-products. Journal of the American Water Works Association 81 (8):54 (1989). 

Young, M. S., D. M. Mauro, P. C. Uden, and D. A. Reckhow. The formation of nitriles and 
related halogenated disinfection by-products in chlorinated and chloraminated water; application 
of microscale analytical procedures. Preprints of papers presented at 210th American Chemical 
Society (ACS) National Meeting, Chicago, IL, American Chemical Society: Washington, D.C., 
pp. 748-751, 1995. 


319 


CONCLUSIONS 


This Nationwide DBP Occurrence Study revealed that many of the high priority 
DBPs can occur in finished drinking water at levels similar to those of the commonly 
measured DBPs. For example, iodo-THM levels ranged from 0.2 to 15 pg/L and 
brominated nitromethane levels were as high as 3 pg/L. In addition, MX levels measured 
in this study were significantly higher than previously reported. Specifically, MX levels 
were often above 100 ng/L, with a maximum concentration of 310 ng/L; brominated 
forms of MX (BMX-1 and BEMX-3) reached 170 and 200 ng/L, respectively. These 
results suggest that some of the high priority DBPs should be the focus of new health 
effects research, particularly for the bromonitromethanes that are being shown to be 
significantly more genotoxic in mammalian cells than MX and most currently regulated 
DBPs. It has also been hypothesized that the iodinated species may be more carcinogenic 
than the brominated species. Given the levels of iodo-THMs that can be formed in 
waters high in bromide/iodide, it is recommended that the iodo-THMs also be targeted 
for expanded/accelerated health effects studies. 

Several haloamides were quantified for the first time in this study and found to be 
present at levels similar to other commonly measured DBPs (low pg/L levels). This is a 
new class of DBP that has not been previously measured in treated, potable waters, and 
may be important due to the levels found. 

With respect to treatment processes, we found that the use of ozone removed MX- 
analogue precursors, and that GAC filters removed MX-analogues via adsorption and/or 
biodegradation. However, it was also shown that post-chlorination or chloramination 
following GAC filtration can contribute to MX-analogue re-formation. Chlorine and 
C102-chlorine were confirmed as the major producers of MX-analogues, as previously 
observed by Kronberg (1999). MX did not form from CIO 2 disinfection per se, rather 
CIO 2 oxidation did not destroy MX precursors (as ozone, another alternative disinfectant, 
does). The high concentrations of MX-analogues (>100 ng/L) observed in these water 
treatment plants were greater than that previously reported. Either previous methods for 
the detection of MX-analogues (all published concentrations <90 ng/L) may have 
systematically underestimated the true concentrations, due to degradation of the MX- 
analogues during lengthy sample storage and processing, or higher concentrations were 
detected in this study because utilities that treat waters high in TOC and/or bromide were 
included. 

This study has also revealed that some of our previous understanding of the 
formation and control of DBPs with alternative disinfectants was not complete. For 
example, it has been assumed from past THM data that alternative disinfectants are a 
good means of controlling other potentially hazardous, halogenated DBPs. However, the 
results show here that some DBPs—particularly iodo-THMs and dihaloacetaldehydes— 
can occur at higher concentrations in treatment plants using alternative disinfectants. 

Thus, while alternative disinfectants can control the formation of the four currently 
regulated THMs, they do not necessarily control all halogenated DBPs of concern. 
Consider that MX was found at its highest level at a treatment plant that disinfected a 


320 


high-TOC water with chlorine dioxide, chlorine, and chloramines. Alternatively, at 
another plant that treated the same water with ozone, biodegradation (on GAC filter), and 
chlorine, halogenated furanone formation was significantly lower. As discussed above, 
this probably reflects differences in the ability of CIO 2 and ozone—as well as 
biodegradation and GAC filtration—to destroy MX precursors, which were probably 
quite high in this high-TOC water. 

Many new DBPs were identified through the course of this study. In particular, 
iodinated acids were identified for the first time, along with a DBP tentatively identified 
as iodobutanal. Therefore, iodo-THMs are not the only possible iodinated DBPs that can 
form. Several new brominated acids were also identified, with carbon chain lengths of 
three and four being common, as well as the presence of diacids and double bonds in 
their structures. One of the high priority DBPs that was quantified in this study—3,3- 
dichloropropenoic acid—is an example of a chlorinated, three-carbon acid; it was 
frequently found in treated waters at levels ranging from 0.4 to 1.5 pg/L in finished 
waters. Therefore, the presence of haloacids other than the regulated, two-carbon 
haloacetic acids must be realized. 

The stability of DBPs in potable water distribution systems and in simulated 
distribution system (SDS) tests varied. In most cases where chloramination was used for 
disinfection, the DBPs were relatively stable. However, when free chlorine was used, 
THMs and other DBPs, including haloacetic acids, increased in concentration in the 
distribution system and in SDS testing. Haloacetonitriles generally were stable (at the 
distribution-system pH levels encountered in this study) or increased in concentration in 
the distribution system, but many of the haloketones were found to degrade. 
Halonitromethanes and dihaloacetaldehydes were also generally found to be stable in 
distribution systems. MX analogues were sometimes stable and sometimes degraded 
somewhat in the distribution system and during SDS testing. When MX analogues 
showed some degradation in the distribution system, they were generally still present at 
detectable levels, indicating that they do not completely degrade. Many times, the 
brominated analogues of MX (BMXs) were stable in the distribution system. 


321 


APPENDIX 


- 322 - 


EXPERIMENTAL METHODS 


CHEMICAL STANDARDS (for Methods Developed at MWDSC) 

When commercial standards were not available, standards were synthesized for the 
project. The initial phase of the project required a survey of chemical companies to obtain as 
many of the target compounds as possible. The remaining compounds were then synthesized. 
This led to a step-wise approach to incorporating compounds as they became available for 
analysis. When synthesized materials were prepared in less than 10-mg allotments, additional 
standards were sometimes needed later in the project. 

At Metropolitan Water District of Southern California (MWDSC), multiple methods 
were used to test for DBPs. It was necessary to make up two independent sets of stock solutions, 
in methyl tertiary butyl ether (MtBE) and methanol, depending on the solvent requirements of 
each technique. Each “pure” standard from the MtBE set was characterized individually to 
determine whether there were any impurities, to note what the impurities were and at what level 
(percentage). Many of the discovered impurities were, in fact, other DBPs. When all the 
standards were combined into spiking solutions, any additionally added DBPs (impurities) had to 
be accounted for through the use of correction factors, either to the final results or to the 
standards being used to generate calibration curves. When correction factors were applied, 
reported concentrations were more accurate because they reflected the true composition of the 
combined set of calibration standards. 


Stock Solutions 

Several commercially available certified standards and mixes were purchased (Table 1). 
These mixes were spiked directly or used to create additional compound class mixtures for 
calibration purposes and spikes of unknown samples. 

Typically, at the beginning of each quarter, new stock solutions were prepared in MtBE 
and methanol. In September 2000, the first set was created that would last through the Fall 2000 
quarter’s sampling. The next set of stock solutions covered all of the Winter 2001 quarter and 
the samples from early Spring 2001. Another set was created in May 2001 and was used through 
the end of the year, covering both Summer and Fall 2001 quarter’s samplings. The last set of 
stock solutions was made in January 2002, and was used with the final phase of sampling in the 
Winter 2002 quarter and an early Spring 2002 sampling. 

The MtBE-diluted compounds were tested in full-scan mode to verify the electron impact 
(El) mass spectrum of the pure compound and also to check for impurities or degradation 
products present (Figures 1-7). As part of an on-going check of the standards, the individual 
stock solutions would be periodically checked to note any changes in the calculated purity or the 
impurities present. Initially, the solutions were checked every 4-6 weeks. Subsequently, after 
approximately 3 month’s usage, new stock solutions would be created, and the previous set 
stored for future reference. 


323 


Table 1. Certified commercial standards used at MWDSC 



Standards Used in Method 3 

Certified Mixes 

Compound 

LLE-GC/ECD 

P&T-GC/MS 

SPE-GC/MS 

Bromochloromethane 





Supelco 4-8067 

2000 lag/mL in methanol 

Bromochloromethane 


X 


Carbon Tetrachloride 

Supelco 40360-U 

5000 iig/mL in methanol 

Carbon tetrachloride 


X 


Chloral Hydrate 

Supelco 4-7335-U 

1000 ug/mL in acetonitrile 

Chloral hydrate 

X 



Dibromomethane 





Supelco 4-8339 

2000 w g/mL in methanol 

Dibromomethane 


X 


EPA 524.2 Fortification Solution 

4-Bromofluorobenzene 


X 


Supelco 47358-U 

1,2-Dichlorobenzene-d4 


X 


2000 iig/mL in methanol 

Fluorobenzene 


X 


EPA 551B Halogenated Volatiles 

Bromochloroacetonitrile 

X 


X 

Supelco 4-8046 

Chloropicrin 

X 


X 

2000 ^g/mL in acetone 

Dibromoacetonitrile 

X 


X 

or 

Dichloroacetonitrile 

X 

X 

X 

HCM-551B (Ultra Scientific) 

1,1-Dichloropropanone 

X 

X 

X 

5000 jig/mL in methanol 

Trichloroacetonitrile 

X 


X 


1,1,1-Trichloropropanone 

X 

X 

X 

EPA 624 Calibration Mix B 

Bromomethane 


X 


Supelco 46967-U 

Chloroethane 




2000 ^g/mL in methanol 

Chloromethane 


X 



T richlorofluoromethane 





Vinyl chloride 




Methyl Tert-Butyl Ether 

Supelco 4-8483 

2000 u g/mL in methanol 

Methyl tert -butyl ether 


X 


Trihalomethane Calibration Mix 

Bromodichloromethane 

X 

X 

X 

Supelco 4-8140-U, 2000 ^g/mL in MeOH 

Bromoform 

X 

X 

X 

or 

Chloroform 

X 

X 

X 

THM-521 (Ultra Scientific) 

5000 ug/mL in methanol 

Dibromochloromethane 

X 

X 

X 

2-Butanone 

Supelco 4-8877 

2000 |ig/mL in MeOH/H 2 0 90:10 

Methyl ethyl ketone 


X 



a LLE-GC/ECD: Liquid/liquid extraction-gas chromatography/electron capture detection 

P&T-GC/MS: Purge-and-trap - GC/mass spectrometry 
SPE-GC/MS: Solid-phase extraction - GC/MS 


324 





















010302A 

100} 


t %- 


DCIM 


Magnet EI+ 
TIC 
2.78e7 


' i' ■ rrr-i' i''' • i''' —pf*n — 1 ' '■ t ''' i 1 


i 11 ' t v 7-1 1 — n r ^n-i ,rri ■ i— r n— r n 


010302B 

100 -] 


%- 


T T 1 - 1 1 I ' 


h ' n' “ 


BCIM 


Magnet EI+ 
TIC 
5.63e7 


n -1 —i ■ 1 1 1 1 


' i " ' i • 1 1 • 


' I 11 I 1 1 1 I 1 1 I - r ~T T 


I 1 1 1 I • 11 I 1 1 'I 

Magnet EI+ 
TIC 
6.35e7 


010302C 

10(h 


%- 


1 1 ■ " 1 i 1 ■ ■ ■ i 1 


T-T .--■■■T -■ | f 


DBIM 


rr— n — 1 i T—^ i' ' i " ' i-r—' —i— r i— r n 

Magnet EI+ 

CDIM 3.24e7 


010302D 

100-1 


%- 


■t . . 


010302E 


h 1 n 1 n r 


Magnet EI+ 



Figure 1. Full-scan total ion chromatograms of iodomethanes from January 2002 stock solution. DBP abbreviations provided 
in Table 2. 


325 


























010902C 



Magnet EI+ 
TIC 
3.12e7 


010902D 



Magnet EI+ 
TIC 
1.67e7 


011002A 

100-1 


%- 


BDCAN? 


Magnet EI+ 
TIC 
2.19e7 


010902G 

100-1 


O+n- 

010902E 

lOOn 


z, DBCAN 

< 


-d 

CQ 


TBAN 


Magnet EI+ 
TIC 
1.40e7 


Magnet EI+ 
TIC 
3.16e7 



O-W 


i Time 


Figure 2. Full-scan total ion chromatograms for haloacetonitriles from January 2002 stock solution; 

a poor result for bromodichloroacetonitrile required the use of the May 2001 stock solution. DBP abbreviations provided in 
Table 2. 






















010802A 

10 *] I CP 


L 


010802B 

100i 


%- 


010802C 

lOO-i 


Q 


—“ i 


Magnet EI+ 
TIC 
3.38e7 


i 



1,3-DCP 


i t 1 t 


"P T" ' . ■ • I ■ ' 1 1 , ' ■ I 

Magnet EI+ 
TIC 
4.35e7 


1,1,3-TCP 


i i " " n . . . . . . 

Magnet EI+ 
TIC 
4.88e7 


%- 


I ' ' ' 1 I-t -r- 


-r-r ' .' 11 i.i- t— i . i ' '—t 


T”-p-- r-, -p-r-r,-rp 

Magnet EI+ 
TIC 
5.59e7 


010802E 

lOO-i 


%- 


1,1,3,3-TeCP 


~l -T 1 -1..' I ' ' ' ' ' ' l - F T r 


'i 1 ' i 1 — l r 


010802D 


0- 

1,1,1,3-TeCP 

: 1 

O '-- 1 ' i '---i-n - -1— .. i... p- ----■ 1111 -T" 1 -- - i.i- "p -'i*.. i 1 M - -n - ir 

-.. , rjl .... .... . ^ 


Magnet EI+ 
TIC 
6.17e7 


Time 


10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50 40.00 42.50 45.00 47.50 50.00 52.50 55.00 


Figure 3. Full-scan total ion chromatograms of chloropropanones from January 2002 stock solution. DBP abbreviations 
provided in Table 2. 


327 





















010802G 



Magnet EI+ 
TIC 
3.03e7 


010802F 


Magnet EI+ 



100i 


O' . . 


1,1,3,3-TeBP 4.24e7 


I— ' 1 —i Time 


Figure 4. Full-scan total ion chromatograms of bromopropanones from January 2002 stock solution. DBP abbreviations 
provided in Table 2. 


328 



















0107C 

100 - 

■ %- 

o- 

0107C 

100 - 

%- 

)2H Magnet EH 

| CNM ,,25 

1. 

[■ ' ■ f ■ i 1 ■ ■ • i ■ - T ■ i ■ ■ ■ ■, ■ ■ i ■ • i. n ^ ' n ' 1 r—^ — 1 ■ i 1 • ■—• ■ ■, ■ ■ i ■ > • i • 1 ■■n-mt-p-i > > 1 ■ < < <> >1 ■ > |i-> ■ - 1 —1 - 1 — 1 —< • • < ■ .—|—•- 

)2G Magnet EI+ 

. RNM tic 

\ 108e7 

0107C 

100 - 

%- 

)2F Magnet EH 

1 OCNM ,jg 

i , 

0107C 

100 - 

%- 

>2E Magnet EI+ 

1 BCNM 

0107C 

100 - 

%- 

p tt 1 .11 ....... 1 .... 1 ■ f 1 11 1 ' ■ 1 , ■ ■ i - n ' \ r ■'. ! — n, r 11 ■p" T ." , T| * 1 r'.. p..« 111 .. 1 • ^Vi- 7 -f ■ 1 • • 1 ■ - •, •—r 1 r —n— t '-*1 ■ ■ 1 ■ ^ 

)2D Magnet EH 

1 DBNM * 1 ,37e7 

11 1 1 t 

0107C 

100 - 

%- 

)2C Magnet EH 

1 BDCNM 22 $ 

0107C 

100 - 

%- 

)2B Magnet EH 

1 DBCNM 3.1 ie7 

0107C 

10 O 

% 

)2A Magnet EI+ 

I TBNM 2 85e7 

! 

10 

1 ■ ■ ■ ■ ■ • ' 1 r 1 1 1 ' 11 1 '' ,_T T' 1 ! 'H ri n ' T '' 1 n— ri 1 h : i ~ r ~i r ' 1 '' 1 '; ’ ' 1 ■ ■ ■ p ■ ■ 1 ■ ■ n ■ ■ 1 ■ ■ . § . . ■ ■ 1 1 ^ 1 ■ ■■!■■■ p r r ' - ' p p 1 1 ■' 1 1 Time 

00 1 2.50 1 5.00 1 7.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50 40.00 42.50 45.00 47.50 50.00 52.50 55.00 


Figure 5. Full-scan total ion chromatograms of halonitromethanes from January 2002 stock solution. DBP abbreviations 
provided in Table 2. 


329 






























010402E Magnet EI+ 



Figure 6. Full-scan total ion chromatograms of haloacetaldehydes from January 2002 stock solution; peaks marked with an 
“x” are solvent impurities. DBP abbreviations provided in Table 2. 


330 



















0+"T 

010402D 

100-1 


%- 


TeBCE 


0 1 ' | - -- . .-. T- 'r. r T 


I 1 ' " I I 1 ,T ~ ' ' 1 ■ '-' I ' 1 ' ' I ' 1 ' ' l ' ' ' I ' ' ' 1 I ' 1 ' I ' I .I ■ ■ ' I 


T 


10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50 40.00 42.50 45.00 47.50 50.00 52.50 


Figure 7. Full-scan total ion chromatograms of miscellaneous compounds from January 2002 stock solution. DBP 
abbreviations provided in Table 2. 


1 ■ i 

Magnet EI+ 
TIC 
7.71e7 


r -^—i Time 
55.00 


331 














Many of the additional peaks present in the pure compounds resulted from the synthesis 
procedure, where yields were less than 100 percent. Alternatively, some of the initially pure 
compounds may have been unstable and degraded over time, forming degradation products, 
some of which were other DBPs. In addition, some “impurities” were attributed to radical 
reactions or thermal lability of some compounds in the hot injection port and/or oven of the gas 
chromatograph (GC) (see section on GC Conditions below). 

To obtain the highest accuracy in quantitation, the compound purities were taken into 
account to determine proper concentration values for standards. Thus, a 1.0 mg sample quantity 
weighed and diluted to 1.0 mL with solvent produced a 1000 mg/L stock solution. In the case 
that the compound was 90 % pure, the effective concentration of the stock solution was 900 
mg/L. 


Tables 2-4 detail DBP purities presented by chemical class. The identification for the 
impurities for the Winter 2002 quarter stock solutions is presented in Table 2. From the 
information in Table 2, combined chemical class mixtures were prepared at lower levels, such as 
50 mg/L for solid-phase extraction (SPE). These individual master solutions were the spiking 
solutions used for standards preparation and also for the spiking of samples. The entire 47- 
compound set for SPE method development was achieved by combining six sets of mixtures that 
generally contained a particular chemical class. This approach was superior to quantitating 
individual compounds for every analysis. In addition, compound classes like the 
halonitromethanes, which had a propensity to degrade faster than other compound classes, could 
be made up more often as needed. Also, calibration curves could be prepared, which just 
included specific chemical classes, when more in-depth probing of sample concentrations was 
necessary. 

Correction Factors 

There are several ways to correct for concentration anomalies with the standards: 

(1) Calculate the actual concentration of each standard and apply it to the data analysis software. 

(2) Calculate the actual concentration of each standard and generate accurate calibration curves 
by hand for each compound of interest. (3) Determine the adjustment necessary to correct a 
standard and apply a correction factor to the final results. The first solution is by far the best 
because it applies the correction to standards early on in the data analysis process, and all 
subsequent samples are referenced against the correct curves. This was eventually applied to 
data generated using the Varian Star Workstation software for results of purge-and-trap (P&T) 
gas chromatography/mass spectrometry (GC/MS) and SPE-GC/MS. The second solution is 
extremely time-consuming because all raw areas need to be transported to an alternative software 
package for graphing purposes. This approach is necessary if the analysis software does not 
allow customization of individual concentration levels. The third solution is the quickest and 
easiest to implement because it looks at the overall adjustment for each of the standards and 
corrects the sample values after the fact. 


332 


Table 2. Making of stock solutions in MtBE for Winter 2002 Quarter 


Compound 

Abbreviation 

Stock 

Weight 

Cone. 

Checked 

Purity 

Adjusted 

Impurities 



Date 

mg 

(mg/L) 

Date 


Cone. (mq/L) 


THM/551B Mix 









Chloroform (trichloromethane) 

TCM 

..... 


5000 

..... 

99+% 

5000 


Bromodichloromethane 

BDCM 

_ 


5000 

_ 

99+% 

5000 


Dibromochloromethane 

DBCM 

_ 


5000 

_ 

99+% 

5000 


Bromoform (tribromomethane) 

TBM 



5000 

_ 

99+% 

5000 


Dichloroacetonitrile 

DCAN 

__ 


5000 

_ 

99+% 

5000 


Bromochloroacetonitrile 

BCAN 

_ 


5000 

.. .. 

99+% 

5000 


Dibromoacetonitrile 

DBAN 

_ 


5000 

___ 

99+% 

5000 


T rich loroacetonitrile 

TCAN 

_ 


5000 

_ 

99+% 

5000 


1.1-Dichloropropanone 

1.1-DCP 

_ 


5000 

_ 

99+% 

5000 


1.1.1 -T richloropropanone 

1.1.1-TCP 

_ 


5000 

_ 

99+% 

5000 


Chloropicrin (trichloronitromethane) 

TCNM 

_ 


5000 

_ 

99+% 

5000 


lodomethane Mix 









Dichloroiodomethane 

DCIM 

12/27/01 

6.7 

6700 

1/3/02 

93.3% 

6250 


Bromochloroiodomethane 

BCIM 

12/27/01 

7.1 

7100 

1/3/02 

96.7% 

6850 


Dibromoiodomethane 

DBIM 

12/27/01 

8.0 

8000 

1/3/02 

97.2% 

7800 

BDIM (2.8%) 

Chlorodiiodomethane 

CDIM 

12/27/01 

5.3 

5300 

1/3/02 

86.3% 

4550 

TIM (2.2%) 

Bromodiiodomethane 

BDIM 

12/27/01 

7.1 

7100 

1/3/02 

91.5% 

6500 

DBIM (4.3%). TIM (4.1%) 

Iodoform (triiodomethane) 

TIM 

12/27/01 

4.3 

4300 

1/3/02 

99+% 

4300 


Haloacetonitrile Mix 









Chloroacetonitrile 

CAN 

12/27/01 

2.8 

2800 

1/9/02 

99+% 

2800 


Bromoacetonitrile 

BAN 

12/27/01 

5.3 

5300 

1/9/02 

99+% 

5300 


T ribromoacetonitrile 

TBAN 

12/27/01 

6.6 

6600 

1/9/02 

99+% 

6600 


Bromodichloroacetonitrile 

BDCAN 

4/6/01 

2.4 

2400 

1/16/02 

91.0% 

2200 

CT (4.0%), DCAN (2.5%) 

Dibromochloroacetonitrile 

DBCAN 

12/27/01 

6.8 

6800 

1/9/02 

41.1% 

2800 

TBAN (36.3%), DBAN (16.7%). TBM (6.0%) 

Haloketone Mix 









Chloropropanone 

CP 

12/28/01 

4.1 

4100 

1/8/02 

98.1% 

4000 

1.1-DCP (1.9%) 

1,3-DichloroDropanone 

1.3-DCP 

12/28/01 

6.2 

6200 

1/8/02 

99+% 

6200 


1.1,3-T richloroDroDanone 

1.1.3-TCP 

12/28/01 

4.2 

4200 

1/8/02 

97.7% 

4100 

1.1.3.3-TeCP (2.3%) 

1.1,3.3-T etrachloropropanone 

1.1.3.3-TeCP 

12/28/01 

6.0 

6000 

1/8/02 

94.9% 

5700 

1.1.1.3-TeCP (2.2%) 

1.1.1,3-T etrachloropropanone 

1.1.1.3-TeCP 

12/28/01 

6.0 

6000 

1/8/02 

91.7% 

5500 


1-Bromo-1.1-dichloroorooanone 

1.1.1-BDCP 

12/28/01 

4.5 

4500 

1/8/02 

76.2% 

3450 

CT (7.2%) 

1.1 -Dibromopropanone 

1.1-DBP 

12/28/01 

5.5 

5500 

1/8/02 

94.1% 

5200 


1.1.1 -Tribromoprooanone 

1.1.1-TBP 

12/28/01 

6.2 

6200 

1/8/02 

98.6% 

6100 


1.1,3-T ribromopropanone 

1.1.3-TBP 

12/28/01 

6.6 

6600 

1/9/02 

99.2% 

6550 


1,1,3,3-Tetrabromopropanone 

1.1.3.3-TeBP 

12/28/01 

4.0 

4000 

1/9/02 

99+% 

4000 


Halonitromethane Mix 









Chloronitromethane 

CNM 

12/27/01 

4.3 

4300 

1/7/02 

98.8% 

4250 

DCNM (1,2%) 

Bromonitromethane 

BNM 

12/27/01 

7.3 

7300 

1/7/02 

99+% 

7300 


Dichloronitromethane 

DCNM 

12/27/01 

4.1 

4100 

1/7/02 

99+% 

4100 


Bromochloronitromethane 

BCNM 

12/27/01 

5.2 

5200 

1/7/02 

89.5% 

4650 

DBCNM (8.1%). DBNM (2.4%) 

Dibromonitromethane 

DBNM 

12/27/01 

5.9 

5900 

1/7/02 

76.9% 

4550 

TBNM (23.1%) 

Bromodichloronitromethane 

BDCNM 

12/27/01 

5.5 

5500 

1/7/02 

99+% 

5500 


Dibromochloronitromethane 

DBCNM 

12/27/01 

6.2 

6200 

1/7/02 

99+% 

6200 


Bromooicrin (tribromonitromethane) 

TBNM 

12/27/01 

7.4 

7400 

1/7/02 

99+% 

7400 


Haloacetaldehvde Mix + Misc. 









Dichloroacetaldehvde 

DCA 

12/28/01 

5.3 

5300 

1/4/02 

99+% 

5300 


Bromochloroacetaldehvde 

BCA 

12/28/01 

1.4 

1400 

1/4/02 

50.1% 

700 

DCA (47.7%) 

T ribromoacetaldeh vde 

TBA 

12/28/01 

7.5 

7500 

1/4/02 

99+% 

7500 


Tribromochloromethane 

TBCM 

12/28/01 

6.1 

6100 

1/4/02 

92.4% 

5650 


Carbon tetrachloride 

CT 

12/28/01 

4.7 

4700 

1/4/02 

99+% 

4700 


1.1.2.2-Tetrabromo-2-chloroethane 

1.1.2.2-TeB-2-CE 

12/28/01 

6.0 

6000 

1/4/02 

92.1% 

5550 


Benzvl chloride 

BC 

12/28/01 

3.3 

3300 

1/4/02 

99+% 

3300 



333 



















































































Table 3. Correction factors for Winter 2002 Quarter when all standards were used 


Compound 

Purity 

Impurities 

Contributions for a 10 pq/L Standard 

Corrected 

Correction 





"10 Std" 

Factor 

THM/551B Mix 






Chloroform 

99+% 





Bromodichloromethane 

99+% 





Dibromochloromethane 

99+% 





Bromoform 

99+% 


1.46 oob from DBCAN 

11.46 

L15 

Dichloroacetonitrile 

99+% 


0.27 oob from BDCAN 

10.27 

1.03 

Bromochloroacetonitrile 

99+% 





Dibromoacetonitrile 

99+% 


4.06 ppb from DBCAN 

14.06 

1.41 

Trichloroacetonitrile 

99+% 





1.1 -Dichloropropanone 

99+% 


0.19 oob from CP 

10.19 

1.02 

1.1.1 -T richloropropanone 

99+% 





Chloropicrin 

99+% 





lodomethane Mix 






Dichloroiodomethane 

93.3% 





Bromochloroiodomethane 

96.7% 





Dibromoiodomethane 

97.2% 

BDIM (2.8%) 

0.47 oob from BDIM 

10.47 

1.05 

Chlorodiiodomethane 

86.3% 

TIM (2.2%) 




Bromodiiodomethane 

91.5% 

DBIM (4.3%). TIM (4.1%) 

0.29 ppb from DBIM 

10.29 

1.03 

Iodoform 

99+% 


0 25 ppb from CDIM; 0.45 ppb from BDIM 

10.70 

1.07 

Haloacetonitrile Mix 






Chloroacetonitrile 

99+% 





Bromoacetonitrile 

99+% 





Tribromoacetonitrile 

99+% 


8.83 oob from DBCAN 

18.83 

1.88 

Bromodichloroacetonitrile 

91.0% 

CT (4.0%). DCAN (2.5%) 




Dibromochloroacetonitrile 

41.1% 

TBAN (36.3%), DBAN (16.7%), TBM (6.0%) 




Haloketone Mix 






Chlorooropanone 

98.1% 

1.1-DCP (1.9%) 




1.3-Dichloroorooanone 

99+% 





1.1,3-T richloropropanone 

97.7% 

1.1.3.3-TeCP (2.3%) 




1.1,3.3-T etrachloroorooanone 

94.9% 

1.1.1.3-TeCP (2.2%) 

0.24 oob from 1.1.3-TCP 

10.24 

1.02 

1.1.1.3-T etrachloroorooanone 

91.7% 


0 23 oob from 1.1.3.3-TeCP 

10.23 

1.02 

1 -Bromo-1,1 -dichloropropanone 

76.2% 

CT (7 2%) 




1.1 -Dibromoorooanone 

94.1% 





1.1.1 -T ribromoorooanone 

98.6% 





1.1.3-Tribromoorooanone 

99.2% 





1.1,3.3-T etrabromoprooanone 

99+% 





Halonitromethane Mix 






Chloronitromethane 

98.8% 

DCNM (1.2%) 




Bromonitromethane 

99+% 





Dichloronitromethane 

99+% 


0.12 ppb from CNM 

10.12 

1.01 

Bromochloronitromethane 

89.5% 

DBCNM (8.1%), DBNM (2.4%) 




Dibromonitromethane 

76.9% 

TBNM (23.1%) 

0.27 ppb from BCNM 

10.27 

1.03 

Bromodichloronitromethane 

99+% 





Dibromochloronitromethane 

99+% 


0.90 oob from BCNM 

10.90 

1.09 

Bromopicrin 

99+% 


3.00 ppb from DBNM 

13.00 

1.30 

Haloacetaldehvde Mix + Misc. 






Dichloroacetaldehvde 

99+% 


9.52 ppb from BCA 

19.52 

1.95 

Bromochloroacetaldehvde 

50.1% 

DCA (47.7%) 




Tribromoacetaldehvde 

99+% 





T ribromochloromethane 

92.4% 





Carbon tetrachloride 

99+% 


0.94 ppb from 1,1,1-BDCP: 0.44 oob from BDCAN 

11.38 

1.14 

1.1.2.2-TeB-2-CE 

92.1% 





Benzvl chloride 

99+% 






334 



















































































Adjustments were necessary when all compounds were added together into a single 
combined solution (Table 3). The column labeled “Corrected 10 Std" represents the 
concentration of the entire mass of material in a standard that was a sum of all the compounds 
and impurities. The values for each pure standard were corrected in the process of making 
intermediate solutions, such as the 50-mg/L compound class mixture discussed above. For 
example, if the stock solution concentration for chlorodiiodomethane (Table 2) was 5300 mg/L 
and the compound’s purity was 86.3 %, then the actual, rounded concentration of 4550 mg/L was 
used to calculate what was required to produce an exact 50 mg/L intermediate standard. Further 
dilutions were prepared to produce a “10 pg/L” standard. Because of the added impurities, the 
effective concentrations for some compounds were above 10 pg/L. 

When a compound had a 91.0 % purity, 11.0 pg/L of that material was required to 
achieve a concentration of 10 pg/L for the analyte of interest (e.g., bromodichloroacetonitrile 
[BDCAN]); whereas, when a compound had a 41.1 % purity, 24.3 pg/L of that material was 
required to achieve a concentration of 10 pg/L for the analyte of interest (e.g., dibromo- 
chloroacetonitrile [DBCAN]) (Table 3). In terms of the contribution of impurities, for example, 
in Winter 2002, 2.5 % of the BDCAN standard was dichloroacetonitrile (DCAN) and 16.7 % of 
the DBCAN was dibromoacetonitrile (DBAN) (Table 3). Because 11.0 pg/L of the BDCAN and 
24.3 pg/L of the DBCAN materials were required to prepare 10 pg/L standards, the contributions 
of the impurities were in actuality 2.5 % x 11.0 pg/L = 0.27 pg/L DCAN and 16.7 % x 24.3 
pg/L = 4.06 pg/L DBAN. Even though the purity of the standards for DCAN and DBAN were 
each 99+ %, the contributions from the impurities in the BDCAN and DBCAN standards, 
respectively, resulted in the 10 pg/L calibration standard having 10 + 0.27 = 10.27 pg/L DCAN 
and 10 + 4.06 = 14.06 pg/L DBAN. Moreover, in some cases, such as for carbon tetrachloride— 
which was obtained as a high-purity standard—it was also found as an impurity in two of the 
synthesized standards (BDCAN and 1,1,1-bromodichloropropanone [1,1,1-BDCP]). Thus, the 
correction factor for carbon tetrachloride reflected the contributions from the two sources of 
impurity (Table 3). 

The correction factors were applied to samples to correct values obtained with the 
standard calibration curves (Method #3). Alternatively, the factors were applied to the standards 
to graph accurate calibration curves, and the sample values were read directly from the chart 
(Method #1). 

Finally, only those compounds that were measured with an analytical technique were 
counted in the correction factor calculations. For example, several DBPs (e.g., DBCAN) were 
ultimately dropped from the SPE-GC/MS method due to stability issues with the dechlorination 
agent ascorbic acid. Thus, the impurity contributions of DBCAN—tribromoacetonitrile (TBAN) 
(36.3 %), DBAN (16.7 %), and bromoform (tribromomethane, TBM) (6.0 %)—were no longer 
present in the SPE-GC/MS standards. TBAN was also removed from the SPE method, so its 
correction factor did not make any difference. DBAN’s and TBM’s correction factors of 1.41 
and 1.15 were no longer needed with the elimination of DBCAN from the SPE method. Thus, 
each of the analytical methods required a modification of Table 3 to reflect the compounds that 
were being included in each method’s combined standard. 


335 


GC Conditions 


For checking the purity of the standards, the original GC temperature program followed 
the U.S. Environmental Protection Agency (USEPA) Method 551.1 procedure (Munch and 
Hautman, 1995), using a DB-1 capillary column (J&W Scientific/Agilent, Folsom, CA; 1.0 pm 
film thickness, 0.25 mm ID x 30 m). Initially, the following program was used: hold at 35°C for 
22 min; increase to 145°C at 10°C/min and hold at 145°C for 2 min; increase to 225°C at 
20°C/min and hold at 225°C for 15 min. The GC injector temperature was 200°C, and the 
detector temperature was 290°C. 

An additional temperature ramp to 260°C was eliminated because all of the compounds 
eluted during the third step of the temperature program. In addition, an injector temperature of 
200°C caused significant degradation of some compounds. The injector temperature was set at 
117°C based on an earlier GC method, which prevented the degradation of the thermally labile 
compound bromopicrin (Krasner et al., 1991). Furthermore, it was possible that some of the 
“impurities” found were actually radical reaction products formed in a hot injection port. Chen 
et al. (2002) saw similar behavior to bromopicrin with other trihalocompounds (e.g., the 
trihaloacetonitriles and other trihlonitromethanes). 

The initial purity checks for the study—September 2000 and January 2001—used an 
injector temperature of approximately 115°C, while work continued to refine the GC temperature 
conditions. An updated GC program was adopted for the stock solutions starting with the May 
2001 set. This new method improved chromatography and helped to eliminate some of the 

impurities by further dropping the injection temperature—from 115 to 89°C-as well as 

lowering the oven temperature at which many of the DBPs eluted. The new temperature 
program was as follows: hold at 35°C for 23 min; increase to 139°C at 4°C/min; increase to 
301°C at 27°C/min and hold at 301°C for 5 min. The injector temperature was 89°C. 

Table 4 summarizes the purity checks performed during the study. For 
tribromoacetonitrile, bromodichloroacetonitrile, dbromochloroacetonitrile, and bromopicrin, 
there was no significant change in purity with the switch from EPA Method 551.1’s GC 
temperature program to the updated GC program in May 2001. For other compounds, such as 
the iodomethanes, there was a significant change (improvement) in purity with the updated GC 
temperature program: up to 25 % for iodoform and 37 % for bromodiiodomethane. Most 
compounds improved or stayed the same. Only two compounds appeared to diminish in purity 
after the GC temperature program change: 1,1,3-tribromo-propanone (1,1,3-TBP) and 
bromochloroacetaldehyde (BCA). Some compounds, such as 1,1,3-TBP, have stability issues, in 
general. A fresh standard of 1,1,3-TBP from Helix Biotech provided more pure material to 
complete the last set of Winter 2002 quarter stock solutions. BCA was always problematic 
because synthesized standards always contained a large contribution from dichloroacetaldehyde 
(DCA). The small loss in purity for BCA in May 2001 could have resulted from difficulty in 
quantitation of DCA. 


336 



Table 4. Purity checks of synthesized standards 


Compound 

Source 

Purity 

Sep-00 

Purity 

Jan-01 

Purity* 

May-01 

Status 

Summer-01 

Purity* 

Jan-02 

lodomethanes 

Dichloroiodomethane 

N 

Aqbar b 

Aqbar 

94.7% 

New 85.4% 

90.2% 


93.3% 

Bromochloroiodomethane 

n 

Agbar 

Aqbar 

75.3% 

New 89.7% 

96.4% 


96.7% 

Dibromoiodomethane 

Agbar 

Aqbar 

13.4% 

New 86.5% 

99+% 


97.2% 

Chlorodiiodomethane 

n 

Agbar 

Aqbar 

65.0% 

New 52.7% 

68.3% 


86.3% 

Bromodiiodomethane 

n 

Agbar 

Aqbar 

Gone 

New 56.0% 

93.8% 


91.5% 

Iodoform 

Mallinckrodt, 0 99% 

74.4% 

73.3% 

99+% 


99+% 

Haloacetonitriles 

Chloroacetonitrile 

Aldrich, d 99% 

99+% 

99+% 

99+% 


99+% 

Bromoacetonitrile 

Aldrich. 97% 

99+% 

99+% 

99+% 


99+% 

T ribromoacetonitrile 

UNC 8 

97.2% 

95.2% 

99+% 


99+% 

Bromodichloroacetonitrile 

UNC. 93%. < 10 mo 

92.6% 

92.4% 

94.8% 

Runnino low 

91,0% f 

Dibromochloroacetonitrile 

N 

UNC, 60%, < 10 mg 
UNC, < 10 mq 

41.6% 

36.4% 

42.1% 

Gone 

New 41.1% 

Haloketones 

ChlorooroDanone 

Aldrich. 95% 

96.4% 

88.9% 

98.0% 


98.1% 

1,3-DichloroDroDanone 

Aldrich. 95% 

99+% 

98.4% 

99+% 


99+% 

1.1,3-T richlorooroDanone 

Fluka. 9 85% 

92.0% 

78.1% 

99.6% 


97.7% 

1,1,3,3-T etrachloropropanone 

N 

UNC 

Helix Biotech, h 93.5% 

90.4% 

71.5% 

99.0% 

Running low 

New 96.5% 

94.9% 

1,1,1,3-T etrachloropropanone 

•» 

UNC 

Helix Biotech, 86.0% 

Not available 

66.3% 

92.4% 

Running low 

New 82.7% 

91.7% 

1-Bromo-1.1-dichloroDroDanone 

UNC. 95% 

75.0% 

63.1% 

77.6% 


76.2% 

1,1 -Dibromopropanone 

N 

UNC 

Helix Biotech, 92.5% 

36.0% 

17.0% 

38.4% 

Running low 

New 94.0% 

94.1% 

1,1,1-Tribromopropanone 

n 

Can Syn Corp' 

Helix Biotech, 97.5% 

89.0% 

48.4% 

97.0% 

Running low 

New 98.1% 

98.6% 

1,1,3-Tribromopropanone 

n 

Can Syn Corp 

Helix Biotech, 96.1% 

89.0% 

84.2% 

55.8% 

Gone 

New 97.6% 

99.2% 

1.1,3.3-T etrabromoorooanone 

TCI America,' 98% 

99+% 

99.0% 

99+% 


99+% 


337 



























Table 4 (continued) 


Compound 

Source 

Purity 

Purity 

Purity* 

Status 

Purity 3 



Sep-00 

Jan-01 

May-01 

Summer-01 

Jan-02 

Halonitromethanes 

Chloronitromethane 

Can Syn Corp 

Not available 

Not available 

99+% 

Gone 



Helix Biotech, 97.2% 




New 98.5% 

98.8% 

Bromonitromethane 

Aldrich. 90% 

99.8% 

98.7% 

99+% 


99+% 

Dichloronitromethane 

Can Syn Corp 

99+% 

96.5% 

99+% 



n 

Helix Biotech, 98.6% 




New 99+% 

99+% 

Bromochloronitromethane 

Can Syn Corp 

Not available 

82.8% 

97.4% 

Running low 


M 

Helix Biotech, 87.1% 




New 85.3% 

89.5% 

Dibromonitromethane 

Maiestic Research k 

21.3% 

77.4% 

97.1% 


76.9% 

Bromodichloronitromethane 

Can Syn Corp, < 10 mg 

55.8% 

Not available 




n 

Can Syn Corp, 98.3% 



New 99+% 



n 

Helix Biotech, 95.8% 




New 99+% 

99+% 

Dibromochloronitromethane 

Can Syn Corp, < 10 mg 

Not available 

Not available 




N 

Can Syn Corp, 95.2% 



New 99+% 



ft 

Helix Biotech, 97.1% 




New 99+% 

99+% 

Bromopicrin 

Columbia Orq Chem Co, 1 95% 

97.9% 

95.9% 

99+% 


99+% 

Haloacetaldehydes 

Dichloroacetaldehvde 

TCI America. 95% 

99+% 

92.2% 

99+% 


99+% 

Bromochloroacetaldehyde 

UNC, < 10 mg 

57.2% 

52.0% 

45.3% 

Gone 


" 

UNC, < 10 mq 





New 50.1% 

T ribromoacetaldehvde 

Aldrich. 97% 

99+% 

91.4% 

99+% 


99+% 

Miscellaneous 

Carbon tetrachloride 

Supelco m 99.97% 

99+% 

99+% 

99+% 


99+% 

Tribromochloromethane 

UNC, 90% 

73.4% 

76.4% 

94.9% 

Running low 


n 

Helix Biotech, 90.3% 




New 84.3% 

92.4% 

1,1,2,2-TeB-2-CE 

Can Syn Corp 

Not available 

Not available 

Not available 

78.7% 

92.1% 

Benzyl chloride 

Fluka. 99.5% 

99+% 

99+% 

99+% 


99+% 


a Updated GC Program 

b Agbar: Aigues of Barcelona (Spain) 

c Mallinckrodt (Phillipsburg, N.J.) 

d Aldrich Chemical Company (St. Louis, Mo.) 

e UNC: Synthesized by University of North Carolina at Chapel Hill 

'stock solution from May 2001 

s Fluka Chemical Co. (St. Louis, Mo.) 

h Helix Biotech (New Westminster, B.C., Canada) 

'Can Syn: Synthesized by Can Syn Chem Corp (Toronto, Ont., Canada) 

^Cl America (Portland, Ore.) 

k Majestic Research: Synthesized by George Majetich, University of Georgia (Athens, Ga.) 
'Columbia: Synthesized by Columbia Organic Chemical Co., Inc. (Camden, S.C.) 
m Supelco (Bellefonte, Pa.) 


338 





















Problematic Compounds 


Hexachloropropanone (HCP) and Pentachloropropanone (PCP). Hexachloropropanone 
(HCP) may undergo a haloform-type reaction in the presence of nucleophiles; consequently, it 
can degrade in acetone or methanol. Thus, HCP stock solutions were prepared in MtBE to check 
retention times. HCP and pentachloropropanone (PCP), however, degraded immediately by 100 
% in water under all conditions. Trihalomethyl-ketones may react with hydroxide ions under 
basic conditions, forming a haloform and a carboxylate anion. Thus, HCP should form 
trichloroacetic acid (TCAA) and chloroform. This hydrolysis was investigated by spiking 
distilled water with 30 pg/L of HCP. An aliquot of the 30 pg/L HCP spiked water was acidified, 
extracted, and methylated with a solution of sulfuric acid/methanol. GC analysis showed the 
presence of 29.6 pg/L of TCAA, which was also confirmed by GC/MS. A liquid/liquid 
extraction-GC analysis of another aliquot of the spiked sample showed the presence of 28.6 pg/L 
of chloroform. Thus, the hydrolysis of HCP, forming TCAA and chloroform, was confirmed. A 
similar experiment was not performed with PCP-spiked water. However, the expected 
degradation by-products for this haloketone are dichloroacetic acid and chloroform. 

1,1,2,2-Tetrabromo-2-chloroethane (l,l,2,2-TeB-2CE) and 1,1,1,2-Tetrabromo-2- 
chloroethane (l,l,l,2-TeB-2CE). These compounds presented great difficulty in terms of 
synthesis. A standard of l,l,2,2-TeB-2CE was ultimately available in relatively high purity from 
Can Syn Corp., whereas the l,l,l,2-TeB-2-CE was available at 28 % purity from Can Syn Corp., 
and as a small sample from the University of North Carolina (UNC) (Figure 8). The impurities 
of the first tetrabromochloroethane (TeBCE) sample (Figure 8a) are tribromodichloroethane 
(TBDCE) and pentabromoethane (PBE), based on the elution order of the compounds and also 
on the theoretical isotopic patterns for subsequent losses of bromine from each impurity. 

A second standard from Can Syn Corp contained both TeBCE isomers together. There is 
very little difference between B^CHCB^Cl and BrsCCHBrCl. Both have the same mass, which 
leads to similar retention times, and the two peaks co-eluted, even using the updated GC program 
(Figure 9b). Furthermore, the mass spectra are nearly the same, with the exception that the 
BraCCHBrCl has a small contribution from CBr 3 + (at only about 8 % of the most abundant 
peak). Thus, the “3+1” TeBCE (l,l,l,2-tetrabromo-2-chloroethane) cannot be easily 
distinguished from the “2+2” TeBCE (l,l,2,2-tetrabromo-2-chloroethane). 

A decision was made to test for the l,l,2,2-TeB-2-CE species, in part, because a standard 
of sufficient purity was available. In addition, it was not clear if the compound in the original 
study in which it was identified was the “3+1” or the “2+2” species. Any TeBCE compounds 
that were present would co-elute and be reported as a combined TeBCE result. 


339 




062901B 


100-1 


I %- 


Br 2 CHCBr 2 Cl Sample 


1 | i i i i | i | i i i i | i i i i | i 


1 I 1 1 1 1 I ' 1 1 1 I 1 


072001A 


lOOn 


Br 3 CCHBrCl Sample 


TeBCE 


Magnet EI+ 
TIC 
8.22e7 


TBDCE 


' T ' - ’Ti f 


PBE 


| I ! I I | I f I T-|-T~T T-.1 

Magnet EI+ 
TtC 
3.08e7 


28 %—► 


%- 




■ i 1 ■ ■ 'i* 


r ' m * . . . 1 1 1 1 i 1 1 1 i | 


c) 


1 I 1 1 1 1 I 1 1 1 1 ! 1 1 1 1 I 1 1 1 1 I ' 


' I 1 1 ' 1 I 1 1 1 1 I 1 ' 1 1 I 1 1 1 1 I 1 


082101D 


o- 

UNC Sample 

/a- 



. k . 

0 - 1 ' ' ' 1 ' ITT^I ' 1 ' ft 1 1 I'l i' r r-r.pri'/V |-| i i i pi i . i 1 i i . i 1 i i i r 1 , i i i ... i m i |T-n-r r i j-i-i pTn; ,1 

i'l i I i 111 Min i i‘i . i ' i*i"f 

1 1 f" i i-ri-rTVT-rrrrr,.... .-h 


Magnet EI+ 
TIC 
7.07e7 


i Time 


30.00 32.00 34.00 36.00 38.00 40.00 4200 44.00 46.00 48.00 50.00 5200 54.00 56.00 58.00 60.00 


Figure 8. Total ion chromatograms for TeBCE samples: (a) Original shipment of 1,1,2,2-tetrabromo-2-chloroethane; (b) Target 
compound l,EE2-tetrabromo-2-chloroethane at reported 28 % purity; (c) UNC sample. 


340 






























Figure 9. Expanded view of TeBCE samples: (a) Original shipment of l,l,2,2-tetrabromo-2-chloroethane; (b) Target compound 
l,l,l>2-Tetrabromo-2-chloroethane at reported 28 % purity; 

(c) UNC sample. 


341 













REFERENCES 


Chen, P. H., S. D. Richardson, S. W. Krasner, G. Majetich, and G. L. Glish. Hydrogen 
abstraction and decomposition of bromopicrin and other trihalogenated disinfection byproducts 
by GC/MS. Environmental Science & Technology 36(15):3362 (2002). 

Krasner, S. W., et al. Analytical Methods for Brominated Disinfection By-Products. 
Proceedings of the1990 American Water Works Association Water Quality Technology 
Conference ; American Water Works Association: Denver, CO, 1991. 

Munch, D. J., and D. P. Hautman. Method 551.1. Determination of 
ChlorinationDisinfection Byproducts, Chlorinated Solvents, and Halogenated 
Pesticides/Herbicides in Drinking Water by Liquid-Liquid Extraction and Gas Chromatography 
with Electron Capture Detection. Methods for the Determination of Organic Compounds in 
Drinking Water, Supplement III, EPA-600/R-95/131. Cincinnati, OH: U.S. Environmental 
Protection Agency, 1995. 


342 


SOLID PHASE EXTRACTION-GAS CHROMATOGRAPHY/ 
MASS SPECTROMETRY METHOD 


A solid phase extraction (SPE)-gas chromatography/mass spectrometry (GC/MS) method 
was developed for quantifying several of the targeted DBPs for this study (Figure 1). SPE offers 
an alternative extraction means to conventional liquid-liquid extraction, and the use of a mass 
spectrometric detector provides specificity that is not possible with electron capture detection 
(ECD) included in EPA Method 551.1. With the method developed here, concentration of 100 
mL of drinking water by SPE provided a sufficient concentration factor to achieve low pg/L 
detection. 

EXPERIMENTAL 

Instrumentation 

A Varian Saturn 2000 ion trap mass spectrometer (Varian Analytical Associates Inc., 
Walnut Creek, CA) equipped with a 3800 GC and a CTC A200s autosampler (CTC Analytics, 
Switzerland) was used. Early methods development was performed on a VG TS-250 medium- 
resolution mass spectrometer (VG Tritech - now Micromass, Inc., Manchester, England). A 
Hewlett-Packard/Agilent Model 5890 GC (Palo Alto, CA) was used for separations and was 
partially controlled by an Optic 2 injector (AI Cambridge Ltd., Cambridge, England). Both full- 
scan and selected ion monitoring (SIM) analyses were conducted. 

Sample Preparation 

Varian Bond Elut PPL (Varian Associates, Inc., Harbor City, CA) SPE cartridges were 
used for extraction of drinking water. Certified standard mixtures were obtained from Ultra 
Scientific (North Kingstown, RI). HCM-551B contains the following compounds at a level of 
5000 pg/mL in acetone: bromochloroacetonitrile, chloropicrin, dibromoacetonitrile, 
dichloroacetonitrile, 1,1-dichloropropanone, trichloroacetonitrile, and 1,1,1-trichloropropanone. 
THM-521 mix contains chloroform, bromodichloromethane, dibromochloromethane, and 
bromoform at a level of 5000 pg/mL in methanol. 

For the DBPs investigated in this study, stock solutions were prepared by accurately 
measuring 1.0 mL of methanol (Burdick & Jackson, purge and trap grade, Muskegon, MI) into a 
capped 1.4 mL autosampler vial and weighing it. Approximately 2-3 pL of pure standard were 
pulled into a clean syringe and spiked under the solvent after piercing the septum. The 
additional weight by difference, between 2-5 mg, was used to calculate an approximate 
concentration value. Alternatively, solid compounds were weighed by difference and deposited 
directly into an empty autosampler vial before solvent was added. The septum caps were 
changed before storage of the samples. Using diluted versions of these stock solutions, the 
purity of the stock solutions could be obtained, and adjustments made to the initial calculations 
(see separate section on Standards). 

SPE was performed using a commercially available 12-port Visiprep vacuum manifold 
and 1/8-inch Teflon tubing with weighted stainless steel ends (Supelco Chromatography, 
Bellafonte, PA). Samples (100 mL) were placed in clean and dry 125-mL Erlenmeyer flasks that 
had been rinsed several times in pure water and baked for 1 hour at 130 °C. The Teflon tubing 
was heated for 10 min at 130 °C. 


343 


Rinse Bond Elut PPL cartridge with 
methanol and dichloromethane 



SPE extraction under vacuum using 
transfer line to sample, ~20 mins. 


Water sample, 100 mL 



Elut resin with 2 mL of 50:50 hexane:dichloromethane 
into 3.5 mL clear Mai 



Transfer 0.5 mL to autosampler M'al 



Add 10 pL of 1-Chlorooctane IS 


Transfer the final extract to conical 
autosampler vial (no headspace) 


V 


Analysis by 
GC/MS 


Figure 1. Summary of the SPE-GC/MS method used for analyzing 35+ DBPs in drinking 
water. 


344 


























Six 3-mL SPE cartridges were conditioned by adding two 3 mL aliquots of methanol to 
the cartridge and allowing it to drain under vacuum, followed by two 3 mL aliquots of 
dichloromethane (Mallinckrodt Baker Inc., Paris, Kentucky). The samples were then attached to 
the vacuum manifold using the Teflon tubing and tube adapters. The flow rates were between 2 
and 7 mL/minute for all samples for complete passage of the water through the sorbent. The 
vacuum lines were closed individually upon completion of the water transfer. To avoid loss of 
compounds, the vacuum was not applied to the sorbents any longer than necessary once the 
water had eluted. 

The Teflon tubing from each sample cartridge was removed and the vial rack inserted 
with six 3.5-mL collection vials. Two mL of a 1:1 mixed solvent system of hexane (Aldrich 
Chemical Co., THM grade, Milwaukee, WI) and dichloromethane was used as the elution 
solvent and placed at the top of the sorbent. (It was not possible to use MtBE as a solvent, due to 
the Varian ion trap mass spectrometer being located in a MtBE-free environment in the 
laboratory). The individual manifold valves were opened and 10 drops were allowed to pass 
through the sorbent material. The six samples were eluted sequentially, 10 drops at a time, until 
no solvent was left in the cartridge. To complete the procedure, 0.5 mL of the top portion phase 
was transferred to an autosampler vial capped with a Teflon-lined septum. Ten pL of a 10 mg/L 
1-chlorooctane standard (Chem Service, West Chester, PA) was added as the internal standard. 

Standards and Check Sample 

One advantage of a sector-based mass spectrometer is the dynamic range that can be 
achieved. Unlike an ion trap mass spectrometer, ions are separated in space and do not suffer 
from so-called "space charge" phenomena. Beginning with the first St. Louis/East St. Louis 
sample set (January 2001), a protocol was established that included standards made at the 
following levels: 1.0, 2.5, 5.0, 10, 20, 30, 40, 50, 60, 75, and 100 pg/L in pure water and 
adjusted to pH 3.5 (for initial analyses using the TS-250 sector mass spectrometer). These 
higher values (up from 40 pg/L previously) were used to bracket some of the higher THM 
concentrations that were seen at some earlier utilities. It was not feasible to spike a mixed set of 
DBPs for any given standard because of software processing limitations. Any higher 
concentration data points that were skewing the calibration curve or causing undesirable effects 
were eliminated. Using this method, very linear curves were produced for most of the 43 
compounds analyzed by SPE-GC/MS. 

The “check standard” can either be a newly extracted standard or a reinjection of one of 
the calibration standards. For the early utilities, the original calibration standards were used as 
check standards because it was very important to make sure that the instrument response had not 
drifted over the extended runs of the instrument (up to 38 hours). The final check was typically a 
50 pg/L or 40 pg/L standard that was used to prove the instrument was still responding correctly. 
In this way, the check standard was certifying the run, and not necessarily the method. 

New calibration standards were required to address the inability to use MtBE as the 
primary solvent for the SPE method. Migrating the method to the Varian ion trap mass 
spectrometer also set restrictions on the concentration range of standards that could be run on the 
instrument to avoid saturation of the trap and potential carryover to subsequent samples. Careful 
evaluation of the ion trap's sensitivity at full scan led to the following recommendations for 
standard concentrations: 0.25, 0.50, 1.0, 2.5, 5.0, 7.5, 10, 15, 20, 30, and 40 pg/L. Only the 


345 


range 0.25 pg/L to 30 pg/L would be used for calibration purposes because of a ten-point limit 
with the Star Workstation software. The 40 pg/L standard would be used for optional processing 
should THM concentrations exceed this range. This became an acceptable protocol because all 
DBP concentrations typically were below 40 pg/L, with the exception of chloroform, which was 
later dropped from the SPE method due to co-elution with the 1:1 hexane:methylene chloride 
solvent system. The final check standard and all sample spikes were at a level of 10 pg/L. 

Gas Chromatography 

Prior to June 2001, when the TS-250 sector mass spectrometer was used, the primary 
column was a DB-1, 30-m, 0.25-mm ID column with a 1-pm film thickness (J & W 
Scientific/Agilent, Folsom, CA). The Optic 2, an advanced programmable temperature injector 
unit, was used to develop the EPA method in conjunction with the TS-250 mass spectrometer. 
The unit comes with its own injector replacement for the Hewlett Packard 5890 GC and controls 
the flow of helium carrier gas, the injection temperature, and the split valves. The Optic 2 
injector was set at 110 °C and was operated in a splitless mode with a head pressure of 8.0 psi on 
the column. Injection volume was 3 pL. The temperature program followed EPA Method 
551.1: 1) Hold at 35 °C for 22 min; 2) increase to 145 °C at 10 °C/min and hold at 145 °C for 2 
min; and 3) increase to 225 °C at 20 °C/min and hold at 225 °C for 10 min. 

After June 2001, when the Saturn ion trap mass spectrometer was used, the primary 
column was a DB-1, 30-m, 0.25-mm ID column with a 1-pm film thickness (J & W 
Scientific/Agilent, Folsom, CA). The Model 1079 injector was set at 90 °C and was operated in 
a splitless mode. Injection volume was 3 pL. The temperature program was changed to match 
the LLE-GC/ECD method being developed: 1) Hold at 35 °C for 23 min; 2) increase to 139 °C 
at 4 °C/min; and 3) increase to 301 °C at 27 °C/min and hold at 301 °C for 5 min. This program 
will be referred to as the updated GC program. 

Mass Spectrometry 

Electron ionization (El) spectra show similar fragmentation patterns depending on the 
class of compound (Table 1). Using a defined sample list and methodology, software is capable 
of integrating individual channels to extract out the peaks of interest. After peak integration, the 
resulting areas are used to form calibration curves for each compound, which can then be applied 
to unknown samples. 

Selected ion monitoring was used to achieve greater sensitivity with the TS-250 mass 
spectrometer. Because the DBPs measured are less than a few hundred Daltons in mass and 
contain similar functional groups, it was possible to monitor selected ion traces that comprised 
common fragment ions for all the compounds. This provided a significant enhancement in 
sensitivity for the older TS-250 sector mass spectrometer. 


346 


Table 1. Fragmentation matrix for DBPs measured using selected ion monitoring. A bold 
"X" indicates the quantitation ion; "x c ” is the confirmation peak. A strike through the x 
indicates a false peak. 


Compound 

Identified Fragment In El Spectrum 

Mi r? fi t*. yi ,*z *3 >n ifj< «*? i?s «♦<» • # i n »v,‘ i *r- i<4 is* *t.i \y*, ?a? .*■» y,\ '?& 

H»lorr>*th&f»s 

ChiOfofc'jm 

fVomcklichlorometnan* 
D&rc>*^c hfoistrvttni#*? 
Bromctfccn 

Tnr-rofrv^htorvmor^r^ 

Oi4hkx0‘0d>n *jm«! '.e 

DlbfOrtKrtiUjCltWPQTiii 

C nirxcrt 

Ervwda cdo m 
lodoform 

ft X 

^ it X x 

X X >5 X X 

x ft x X * 

xx v X x 

« X & 

* X ft X 

XXX ft X » « 

ft X x 

* <t X x 

X ft 

H»lo*c*tonltrll»s 

Efomoocwonmik- 

Chiwoorettnieiie 

pKHtotoOMfc-mM* 

Tocfttecoc ei«-nitr;» 
TobromcacMsotltite 

X « < x X x 

X X X. 

ft: X X X 

X X X X X X 

ft < x X x 

* X X 

« X X X X x X 

BfornodKWorofiC 

yxx x xxXx x x ^ 

x <x > x < x X x 

ttttfaksissnsa 

Ct'!9rop«!P3w>n* 

1.1 -OcniOrCFrcpendne 

t .3-0*t!&*CffCoamrte 

1.1.1 .Tn<ihl*repi'e£<5»x»rft 

1.1 3-Trichtorooreoanorw 

X * 

X x x *t 

X M X * 

X i Xc > X X 

X X ft *c 

1. 1 

x X X 

l.t.1.3 J.FWMctft'K'prcpaiwoe 
1 gnjmo- 1.1 '0chtei'‘j()rep«ir*efl» 
1,1 

1 .i^CKOmop'OpafiiXW 
l.t .l.TnpromccrepaflvO# 

1. t .J-Tnorwr^rcfjnWiO 

1.1 3.A 

y X Xt y X 

X X < X X >e » 

X X XX X At X 

X Xc X 

X X >c X XXX 

X X X ft X X XX 

X « i 

Hatoacetaldehydes 

DieMeroaceisIdsivi* 

EWmocnioroeMWSSetvdo 

T0&roma*1*MM*11v4ft 

X > 

X XXX x XL 

* < X X ) X 

attafeamslfema 

Chk*c**trome!tane 

DfCftottnia orr-mtu*** 

Qtix&rxWMWtoM 

Chfcropscnn 

X 

x ft X 

X 

ft x jc x X x 

ft x X X x 

Eteroopjcn* 

P*<«rriO<iK 

D« WofCrijr>>ntoihar«$ 

x *•- x X 

fc X > 3 X 

x * .< x X 

Mlsc. Comooundx 

C Wracfcfiondf 

v X X <■ 

X 


Sample Preservation 

As samples are taken in the field, it is necessary to stop any further DBP formation from 
occurring by adding a quenching agent that can remove residual oxidants. In previous work, 
dilute solutions of ascorbic acid (AA) or ammonium chloride (AC) were added directly to the 
sample vial or bottle. This method works well, provided that the containers are not allowed to sit 
idle for more than a few days. Additionally, past studies have found that by adjusting the pH of 
the sampled water, many DBPs can be stabilized for several weeks, giving a much larger 
window of opportunity for analysis and establishing a better holding time for refrigerated 
storage. 

The method parameters chosen for this study were 31 mg/L of ascorbic acid and enough 
sulfuric acid to lower the pH to 3.5. A solution of 16 mg/L of ascorbic acid was deemed 
necessary to remove 3.0 mg/L of chloramines residual, so 31 mg/L of ascorbic acid in each bottle 
was chosen to have a safety factor. An experiment was performed on Weymouth effluent water 
from the Weymouth Water Treatment Plant (La Verne, CA) using clear 44-mL vials with 1.4 mg 
of ascorbic acid (31 mg/L) and 5 drops of 0.25 M H 2 S0 4 added. The 5 drops were enough to 
fully dissolve the ascorbic acid powder. After several days, however, the contents of the vials 
proved ineffective for quenching fresh samples of water. This posed a problem because the 
ascorbic acid in the acidic solution was degrading. As a result, the ascorbic acid and sulfuric 


347 













acid would have to be separated. Separate additions of ascorbic acid and sulfuric acid was also 
wise because it would be difficult to know the appropriate dose of acid to achieve the required 
pH for water utilities where the buffering capacity of the water was unknown. It was decided 
that an acid kit, which would include an eyedropper bottle with dilute sulfuric acid and pH test 
strips, would accompany each set of ice chests sent to the utilities, so that the sampler operators 
could add the necessary acid in the field. The quenching agent, ascorbic acid, in its granular 
form, would be added to each container at the Metropolitan Water District of Southern California 
(MWDSC) before shipping. For the 125 mL bottles filled for SPE-GC/MS analysis, two 2 mg 
scoops were used to achieve the ~4.0 mg and a solution concentration of 31 mg/L. 

Each utility was given a detailed set of instructions and told not to rinse out the bottles 
(because they contained preservative). Only vials and bottles containing a red cap would require 
pH adjustment with acid. This situation worked out well because when unforeseen delays arose 
for the utility sampling, the bottles could be kept for several weeks both before the sampling and 
after the sampling without compromising the DBP preservation. When samples returned to the 
laboratory, their pH was re-checked and adjusted if necessary. 

Ice Chest Containers 

When each of the ice chests was opened, there was a set of paperwork immediately on 
top (sampling instructions, sample collection sheets, and a return Federal Express label). There 
was a sheet attached to the inside of each ice chest identifying it as belonging to the MWDSC 
and labeling the appropriate utility to which it was sent. Additional information included the 
identification of ice chests intended for simulated distribution system (SDS) samples or 
assimilable organic carbon (AOC) samples. The large ice chests contained four blue ice packs. 
The small ice chests contained one or two ice packs, depending on space. All ice packs were 
shielded from the sample bags by Styrofoam, peanut-filled plastic bags. It was important to 
isolate the cold packs from the samples to prevent freezing of the water and breakage. 

The sulfuric acid solution containers were placed in small white boxes located usually 
along with the SDS ice chests. These acid kits included an eyedropping amber bottle, two 
additional plastic eyedroppers in case of breakage, and a set of pH test strips. 

RESULTS AND DISCUSSION 


Detection Limits 

TS-250 Mass Spectrometer. Because the TS-250 instrument was older and was subject to 
drift during the course of a day’s analysis, calibration standards were run with each set of 
samples to insure the most accurate results. A set of three 10 pg/L standards, comprising 20 of 
the DBPs, were extracted using SPE and analyzed the same day on three separate occasions. The 
results were interpreted for daily standard deviation and for the overall standard deviation for all 
9 samples. The overall standard deviation was multiplied by 2.896 (student t-value for 8 degrees 
of freedom at 98% confidence) to get the approximate method detection level (Table 2). 

A daily precision of 1.1 pg/L was observed for samples that underwent off-line SPE. 
However, when comparisons were made of data taken over multiple days, this variance increased 
to 2.2 pg/L. Overall detection limits were set at 3 pg/L because of the requirement that 


348 


standards be run on a daily basis. This limit appeared reasonable because the instrument was 
capable of detecting 1 pg/L levels. 

The solid phase extraction technique is probably at its limit for reproducibility (for low 
ppb levels). SPE, unlike P&T, is performed manually over the course of several hours. Human 
error will play some role in the extraction process, but there is also a significant time segment 
where the sample is either exposed to a hood environment or direct vacuum, which can 
potentially contribute to the loss of some compounds. 

Errors in quantitation of samples can also occur due to the SIM scan speed of the magnet. 
For SIM acquisition, the dwell time for each m/z measurement must be sufficiently long to 
adequately sample the ion population, but sufficiently short to collect as many samples per 
eluting peak as possible. By setting a residence time of 50 msec per m/z measured and allowing 
time for the magnet to switch to next mass, there is a necessary scan time of 2.17 seconds/scan. 
Often, this amounts to only 5 to 8 samples per chromatographic peak, which can cause errors 
because a peak area approximated by only 5 to 8 data points will be inherently less accurate than 
one sampled by many more points to give better peak resolution. 


Table 2. Detection limit study for selected compounds showing both daily and overall 
standard deviations for a typical 10 pg/L standard . 


Compound 

RT 

(min.) 

A 

4/10 

B 

4/10 

C 

4/10 

D 

4/12 

E 

4/12 

F 

4/12 

G 

4/18 

H 

4/18 

1 

4/18 

Daily 

Std. Deviation 

AVE 

Cone. 

SD 

AVE 

RSD 

% 

Estimated 
MDL, ug/L 

4/10 

4/12 

4/18 

Chloroform 

5.98 

9.0 

9.4 

9.7 

5.9 

6.2 

6.3 

8.6 

9.5 

10.1 

0.4 

0.2 

0.8 

8.3 

1.7 

20 

5 

Dichloroacetaldehyde 

6.20 

17.7 

15.2 

16.2 

13.7 

13.0 

13.9 

9.6 

11.5 

11.2 

1.3 

0.5 

1.0 

13.6 

2.6 

19 

7 

Chloroacetonitrile 

7.46 

9.9 

12.7 

14.7 

11.7 

13.7 

13.3 

8.4 

12.2 

12.4 

2.4 

1.1 

2.3 

12.1 

1.9 

16 

6 

Chloropropanone 

8.15 

6.2 

7.1 

13.3 

12.1 

12.8 

13.5 

11.6 

11.7 

13.9 

3.9 

0.7 

1.3 

11.4 

2.8 

25 

8 

Trichloroacetonitrile 

8.80 

10.3 

10.5 

10.7 

5.6 

6.1 

5.9 

7.7 

8.5 

8.9 

0.2 

0.3 

0.6 

8.2 

2.0 

25 

6 

Dichloroacetonitrile 

10.17 

10.7 

11.1 

12.1 

8.3 

10.0 

10.4 

7.5 

9.0 

10.9 

0.7 

1.1 

1.7 

10.0 

1.5 

15 

4 

Bromodichloromethane 

10.50 

9.3 

9.7 

10.4 

5.8 

6.9 

6.8 

7.8 

8.9 

10.3 

0.6 

0.6 

1.3 

8.4 

1.7 

20 

5 

1.1 -Dichloropropanone 

12.70 

9.1 

9.6 

10.1 

9.2 

10.3 

10.9 

8.0 

9.9 

11.1 

0.5 

0.9 

1.6 

9.8 

1.0 

10 

3 

Bromoacetonitrile 

14.50 

10.6 

12.5 

13.9 

11.9 

13.8 

15.5 

6.5 

9.7 

11.8 

1.7 

1.8 

2.7 

11.8 

2.7 

23 

8 

Chloropicrin 

19.81 

10.5 

10.2 

11.1 

4.6 

5.7 

5.9 

6.9 

8.4 

9.4 

0.5 

0.7 

1.3 

8.1 

2.4 

29 

7 

Dibromochloromethane 

20.61 

10.3 

10.5 

11.4 

5.8 

7.4 

7.6 

6.5 

9.1 

10.7 

0.6 

1.0 

2.1 

8.8 

2.0 

23 

6 

Bromonitromethane 

21.00 

11.6 

12.3 

13.7 

8.3 

11.9 

13.5 

5.9 

9.2 

10.6 

1.1 

2.7 

2.4 

10.8 

2.6 

24 

7 

Bromochloroacetonitrile 

21.26 

11.7 

11.9 

12.8 

7.9 

9.8 

10.0 

6.4 

8.4 

9.9 

0.6 

1.2 

1.8 

9.9 

2.1 

21 

6 

1,1,1 -T richl oropropanone 

26.38 

11.9 

12.2 

12.9 

9.0 

10.4 

10.9 

6.3 

8.6 

10.0 

0.5 

1.0 

1.9 

10.2 

2.1 

20 

6 

1,3-Dichloropropanone 

27.14 

12.5 

13.9 

14.4 

11.2 

12.0 

13.5 

4.8 

8.7 

9.6 

1.0 

1.2 

2.6 

11.2 

3.1 

27 

9 

Bromoform 

28.12 

10.9 

11.2 

12.4 

6.8 

8.7 

8.9 

6.4 

8.7 

10.3 

0.8 

1.2 

2.0 

9.4 

2.0 

21 

6 

Dibromoacetonitrile 

28.48 

12.3 

12.6 

13.3 

7.9 

9.5 

10.0 

6.4 

7.8 

9.2 

0.5 

1.1 

1.4 

9.9 

2.4 

24 

7 

1,1,3-Trichloropropanone 

30.75 

16.4 

14.8 

15.4 

11.3 

11.6 

10.8 

8.3 

9.9 

9.0 

0.8 

0.4 

0.8 

11.9 

2.9 

24 

8 

Benzyl Chloride 

32.66 

10.3 

10.6 

11.6 

6.9 

8.1 

8.4 

5.9 

7.1 

7.8 

0.7 

0.8 

1.0 

8.5 

1.9 

22 

6 

Iodoform 

37.86 

12.4 

12.7 

13.3 

7.2 

8.2 

8.2 

10.2 

9.6 

9.3 

0.5 

0.6 

0.5 

10.1 

2.2 

22 

6 


Averages 


1.0 

1.0 

1.6 


2.2 

21.5 

6.3 


349 




















Extraction Efficiency 

The extraction efficiency of the Bond Elut sorbent was tested at three different standard 
concentrations, 10 pg/L, 25 pg/L, and 50 pg/L, to determine whether there were any sample 
loading concerns with the sorbent’s capacity. Most of the anticipated values for DBPs in 
drinking water would be well below 50 pg/L. Compounds within the same compound family 
exhibited similar extraction efficiencies. The important observations were that recoveries were 
good (74% average) and higher concentrations of analytes, up to 500 pg/L, do not saturate the 
capacity of the Bond Elut sorbent. 

Early Observations 

VOC concentrations can become altered if excessive headspace or high temperatures are 
present. For analysis, the headspace was minimized by using 100 pL conical autosampler vials 
(that hold ~300 pL when filled to top) for storage, rather than the typical 1.4 mL autosampler 
vials. For samples that sit on top of the GC for extended runs, they are exposed to high 
temperatures. A Tekmar water bath circulating system was attached to the sample tray to 
remove some of the heat load. The water bath's temperature was set to maintain a temperature of 
21.0 °C (about room temperature) on the sample tray, which minimized sample 
degradation/volatilization for extended runs. Chloroform and bromodichloromethane showed 
the most improvement for spike recovery. 

The heavier iodo-THMs, haloacetonitriles, and halonitromethanes showed much reduced 
recoveries for 10 ppb-spiked samples. This was either an expected limitation for the SPE 
procedure, or the lower injection temperature used discriminated against these heavier (higher 
boiling point) compounds. Significantly raising the injection temperature, however, would have 
caused many more problems with degrading species. It was discovered later that some of these 
compounds (bromodichloro-, dibromochloro-, and tribromoacetonitrile, and bromodichloro-, 
dibromochloro-, and tribromonitromethane) were not preserved using ascorbic acid. 

Several analytes were found to coelute on the GC. Bromochloroacetaldehyde (retention 
time of 12.6 min.) co-eluted with trichloroacetaldehyde, which was not present in the method, 
but has been seen in many samples and was part of the Information Collection Rule. 

Chloropicrin (retention time of 21.8 min.) co-eluted with bromodichloroacetonitrile. An easy 
separation was achieved by using different quantitation masses — m/z 117 for chloropicrin and 
m/z 108 for bromodichloroacetonitrile. The m/z 117 contribution from 
bromodichloroacetonitrile, if present, was negligible and small enough to ignore. 

Tribromoacetaldehyde (retention time of 32.8 min.) co-eluted with tribromoacetonitrile. 
An alternate quantitation peak, m/z 251, was chosen for tribromoacetaldehyde, at reduced 
sensitivity, to effect a clean separation from tribromoacetonitrile and other nearby species. 
Bromonitromethane was sandwiched between dibromochloromethane and 
bromochloroacetonitrile, which did not allow baseline resolution for that quantitation channel, 
m/z 93. 


Dibromoiodomethane, 1,3-dibromopropanone, tribromoacetaldehyde, and 
tribromoacetonitrile all eluted within 0.1 min of each other. Alternate channels eliminated major 
overlaps, but sensitivity was reduced. Chloro-, 1,1-dichloro-, 1,1,1 -trichloro-, 1,1-dibromo-, 1- 
bromo-l,l-dichloro-, and 1,1,1-tribromopropanone were difficult to quantitate because of 


350 


common fragmentation patterns produced. The highest ion abundance came from m/z 43 
(COCH3), which showed a low level persistent background throughout the run. Another co¬ 
eluting system — dibromoacetonitrile/bromodichloronitromethane (retention time of 33.9 min.) - 
- was eliminated by using different mass channels. Improved chromatography or the use of a 
different polarity column could also correct this problem. 

Choice of Analytical Columns 

CP-1301 Column. The CP-1301 column was installed on the TS-250 mass spectrometer 
to evaluate its performance for separating the targeted DBPs. The GC temperature program was 
the latest that MWDSC had been using, with the exception that this column could not go beyond 
a maximum temperature of 250 °C. This lowered maximum temperature caused a lower overall 
sensitivity for late eluting compounds. 

Peaks that were not baseline-resolved included dichloronitromethane and 
dibromochoromethane, bromoacetonitrile and dichloroiodomethane, and 
bromochloronitromethane and bromoform. Another difficult problem was that of co-eluting 
species, which for the CP-1301 column included: chloroform + others, carbon tetrachloride + 
others, dichloroacetonitrile + bromodichloroacetonitrile, 1,1-dibromopropanone + 
bromochloroiodomethane, and dibromoiodomethane + benzyl chloride. Peaks for 
dichloroacetaldehyde, bromochloracetaldehyde, trichloroacetaldehyde, tribromonitromethane, 
and 1,1,3,3-tetrabromopropanone were not found, or, they were problematic for analysis using 
this column/setup. Bromodichloronitromethane and dibromochloronitromethane were not 
included in this mixture analyzed. Figure 2 shows the CP-1301 column performance for the 
targeted DBPs. 

DB-5 Column. A DB-5 column was installed on the TS-250 mass spectrometer and was 
used to analyze the same spiking mixture. There were a lot of co-eluting peaks, although it was 
clear that trichloroacetaldehyde and bromochloroacetaldehyde were well separated. Another 
benefit of this column was that there was better signal-to-noise, compared to the CP-1301 
column, particularly at the high end of the chromatogram where degradation of compounds and 
column bleed is normally a problem. 

Peaks that were not baseline resolved included bromochloronitromethane and 1,1,1- 
trichloropropanone; 1,1,3-trichloropropanone and tribromochloromethane; and 1,1,1- 
tribromopropanone and bromodiiodomethane. Co-eluting peaks included dichloroacetaldehyde 
+ others; chloroacetonitrile + trichloroacetonitrile; bromonitromethane + 
bromochloroacetonitrile; dibromoiodomethane + tribromoacetonitrile + benzyl chloride; and 
chlorodiiodomethane + 1,1,3,3-tetrachloropropanone. 


351 



Figure 2. CP-1301 column performance using full DBP set. Compounds not detected 
include dichloroacetaldehyde, bromochloroacetaldehyde, tribromoacetaldehyde, 
tribromonitromethane, and 1,1,33-tetrabromopropanone. Compound abbreviations are 
found in Table 3. 


DB-1 Column. As a comparison between the DB-5 column and a DB-1 column, the two 
columns are profiled side-by-side in Figure 3, which shows unambiguous peak identities when 
converting between the two chromatograms. As a general rule, the DB-1 column was preferred 
because, in conjunction with individual mass traces, it allowed for the separation of all the 
targeted DBPs, except for the trichloroacetaldehyde-bromochloroacetaldehyde conflict. In 
general, DB-1 improvements over DB-5 included: a) separation of chloroacetonitrile and 
trichloroacetonitrile, b) separation of bromonitromethane and bromochloroacetonitrile, c) 
separation of bromochloronitromethane and 1,1,1-trichloropropanone, d) separation of 1,1,3- 
trichloropropanone and tribromochloromethane, e) partial separation of dibromoiodomethane, 
tribromoacetonitrile, and benzyl chloride, f) separation of chlorodiiodomethane and 1,1,3,3- 
tetrachloropropanone, and g) separation of 1,1,1-tribromopropanone and bromodiiodomethane. 

DB-624 Column. The DB-624 column used on the Varian Saturn ion trap mass 
spectrometer was very similar in polarity to the CP-1301 column tested. It is the column 
currently used by MWDSC for the EPA Method 524.2 purge-and-trap analyses. Many of the 
heavier DBPs, such as the halonitromethanes were not well recovered from this column, partially 
due to the polarity and lowered maximum temperature. The DB-624 column was replaced with a 
DB-1 column to achieve the same performance, as was being done for the LLE-GC-ECD and 
SPE-GC/MS (TS-250 mass spectrometer) methods. The replacement option made it necessary 


352 


























































Figure 3. DB-5 column versus DB-1 column performance using full DBP set. 


to re-evaluate purge-and-trap operation with a DB-1 column for a more limited set of 
compounds. 

Improved Temperature Program 

The updated GC temperature program was officially adopted in June 2001 for the SPE- 
GC/MS method used on the TS-250 mass spectrometer and all subsequent work on the Saturn 
ion trap mass spectrometer. The updated GC temperature program, along with a lower injection 
temperature of 90 °C was used for the latest set of stock solutions to get new retention times for 
all of the DBPs (Table 3). 

In attempting to translate the retention times obtained from the older results to those 
found by utilizing the updated GC program, it was noted that simple linear equations can be used 
to approximate new retention times. During the first 23 min of the temperature programs, both 
results are the same because both hold the GC oven at 35 °C for the isothermal portion of the 
programs. The correlation of the retention times after 23 min is not a mirror image because of 
the differences in ramp rates between the two temperature programs (see Gas Chromatography 
section above). Figure 4 shows the two linear approximations that can be used for estimating the 
new GC retention times. The equation y = 0.9972x + 0.0699 for the 0 to 23 minute portion of 
the graph is synonymous with y = x, with a very small offset. 


353 











































Table 3. VG TS-250 mass spectrometer quantitation ions for selected ion monitoring and 
elution order before and after update to GC program 


Compound 

Abbreviation 

Quantitation 

Confirmation 

TS-250 Retention Time, Minutes 

TS-250 Retention Time, Minutes 



m/z 

m/z 

(MtBE, 551.1 GC Program) 

(M(BE, Updated GC Program) 

Chloroform 

TCM 

83 

49 

6.80 

6.92 

Dichloroacetaldehyde 

DCA 

49 

83 

7.04 

7.10 

Chloroacetonitrile 

CAN 

75 

77 

8.36 

8.47 

Chloropropanone 

CP 

43 

49 

9.1! 

9.12 

Carbon Tetrachloride 

CT 

117 

49 

9.38 

9.47 

T richloroacetonitrile 

TCAN 

108 

49 

9.79 

9.85 

Dichloroacetonitrile 

DCAN 

74 

49 

11.42 

11.38 

Bromodichloromethane 

BDCM 

83 

79 

11.69 

11.73 

Chloronitromethane 

CNM 

49 

N/A 

_ 

12.42 

Bromochloroacetaldehyde 

BCA 

49 

130 

12.57 

12.57 

1,1 -Dichloropropanone 

DCP 

43 

93 

14.06 

14.08 

Dichloronitromethane 

DCNM 

83 

N/A 

15.01 

14.95 

Bromoacetonitrile 

BAN 

119 

79 

16.16 

16.10 

Chloropicrin 

TCNM 

117 

49 

21.83 

21.83 

Bromodichloroacetonitrile 

BDCAN 

108 

154 

21.90 

21.92 

Dibromochloro methane 

DBCM 

127 

9! 

22.68 

22.73 

Bromonitromethane 

BNM 

93 

79 

23.25 

23.10 

Bromochloroacetonitrile 

BCAN 

74 

N/A 

23.29 

23.52 

Dichloroiodomethane 

DCIM 

83 

127 

25.25 

26.67 

B romo chloro nit romet hane 

BCNM 

129 

79 

26.03 

28.05 

1,1,1-Trichloropropanone 

1.1,1-TCP 

43 

83 

27.08 

30.00 

1,3-Dichloropropanone 

1,3-DCP 

77 

49 

27.80 

31.38 

Bromoform 

TBM 

173 

91 

28.75 

33.12 

Dibromoacetonitrile 

DBAN 

118 

79 

29.05 

33.88 

Bromodichloronitromethane 

BDCNM 

163 

49 

_ 

33.87 

Dibromochloroacetonitrile 

DBCAN 

154 

74 

29.32 

34.28 

1,1 -Dibromopropanone 

1,1-DBP 

43 

173 

29.66 

34.88 

Bromochloroiodomethane 

BCIM 

127 

175 

29.80 

35.18 

Dibromonitromethane 

DBNM 

173 

43 

30.10 

35.93 

1 -Bromo-1,1 -dichloropropanone 

1,1,1-BDCP 

43 

127 

30.88 

37.45 

1,1,3-Trichloropropanone 

1,1,3-TCP 

77 

83 

31.22 

38.25 

T ribromochloromethane 

TBCM 

207 

79 

— 

39.10 

Dibromochloronitromethane 

DBCNM 

207 

79 

_ 

40.92 

Dibromoiodomethane 

DBIM 

173 

127 

32.68 

41.17 

T ribromoacetaldehyde 

TBA 

251 

173 

32.75 

41.40 

T ribromoacetonitrile 

TBAN 

198 

79 

32.82 

41.53 

Benzyl chloride 

BC 

91 

N/A 

33.09 

42.22 

Chlorodiiodomethane 

CDIM 

175 

127 

33.36 

42.62 

1,1,3,3-Tetrachloropropanone 

1,1,3,3-TcCP 

83 

N/A 

33.46 

43.00 

1,1,1,3-Tetrachloropropanone 

1.1.1.3-TeCP 

77 

49 

33.70 

43.53 

Bromopicrin 

TBNM 

251 

91 

35.36 

46.48 

Bromodiiodomethane 

BDIM 

219 

127 

35.94 

47.42 

1,1,1 -T ribromopropanone 

1,1,1 -TBP 

43 

251 

36.14 

47.90 

1,1,3-Tribromopropanone 

1,1,3-TBP 

121 

93 

37.63 

50.70 

Iodoform 

TIM 

127 

267 

38.31 

51.47 

1,1,3,3-Tetrabromopropanone 

1,1,3,3-TeBP 

120 

173 

40.48 

53.75 


The interconversion between the two GC programs was helpful for determining where 
peaks would appear in a chromatogram, and it could be used to check the location of new peaks 
or impurities. The software method used for processing all SIM data was updated on 6/5/01 to 
reflect these new retention times, as well as the new correction factors for the latest set of stock 
solutions. 


354 



































































y = 1.9648X - 23.13 
R 2 = 0.9988 



EPA Method 551.1 Retention Times (min.) 


y = 0.9972x + 0.0699 
R 2 = 0.9998 


▲ 0 to 24 minutes 

• 25 to 40 minutes 

.0 to 24 minutes 

-25 to 40 minutes 


Figure 4. Correlation of retention times before and after GC program update. 


Problematic Compounds 

All subsequent work utilized the DB-1 column for compound separation. 
Chloronitromethane was found to co-elute with bromochloroacetaldehyde (and 
trichloroacetaldehyde). There was no solution available at this time (Figure 5). It may be 
possible to analyze for bromochloroacetaldehyde using only m/z 130 at about 40% of the 
sensitivity of the m/z 49 peak. There was not, however, sufficient quantities of 
bromochloroacetaldehyde to warrant further methods development on the 
bromochloroacetaldehyde and trichloroacetaldehyde co-elution. 

Chloropicrin co-eluted with bromodichloroacetonitrile. Selection of different mass 
channels can eliminate this conflict (Figure 6). Bromodichloroacetonitrile and 
trichloronitromethane can be separated on the DB-5 column. The analysis of 
bromodichloroacetonitrile by SPE-GC/MS was later dropped because it required ammonium 
chloride for a quenching agent and preservative. 


355 
















Figure 5. Chloronitromethane (CNM) co-elutes with bromochloroacetaldehyde (BCA) 
(which co-elutes with trichloroacetaldehyde (TCA)). Chloronitromethane is not amenable 
to SPE-GC/MS analysis. 

Mass Spectra 50 ppb Extracted Standard 


TCNM+BDCAN 



Figure 6. Chloropicrin (TCNM) co-elutes with bromodichloroacetonitrile (BDCAN). Both 
are amenable to SPE-GC/MS analysis. 


356 























































Mass Spectra 


50 ppb Extracted Standard 


BDCNM+DBAN 



Figure 7. Bromodichloronitromethane (BDCNM) co-elutes with dibromoacetonitrile 
(DBAN). Both are amenable to SPE-GC/MS analysis. 


Bromodichloronitromethane co-eluted with dibromoacetonitrile. Selection of alternate 
mass channels eliminates a conflict (Figure 7). However, bromodichloronitromethane was later 
dropped from the SPE method because it too required ammonium chloride as a quenching agent 
and preservative. 

Holding Study 

As was stated in the Early Observations section of this chapter, certain heavier 
haloacetonitriles and halonitromethanes showed consistently poor quantitation in earlier work on 
this project. Before the final year of sampling was to begin, it was necessary to revisit the choice 
of ascorbic acid as a general quenching agent and preservative for all DBPs that were being 
studied by SPE, LLE, P&T, and SPME methods. Many of these compounds were not available 
during the initial methods development period. Thus, an experiment was carried out to evaluate 
the stability of DBPs stored with ascorbic acid at a pH of 3.5. 


357 






































The results were surprising because it was discovered that six compounds were not 
amenable to this ascorbic acid/pH 3.5 combination. To summarize the results by DBP class: 

No problems through Day 21. 

No problems through Day 21. 

No problems through Day 21, except bromodichloro-, 
dibromochloro-, and tribromoacetonitrile showed no recovery 
between Day 0 and Day 3 (Figure 8). 

No problems through Day 21. 1,1 -Dichloropropanone was 
difficult to quantitate. 

No problems through Day 21. 1,1,3-Tribromopropanone had a 
slow decay. 

No problems through Day 21, except 

Bromodichloronitromethane, dibromochloronitromethane, and 
tribromonitromethane showed no recovery. 

Difficult to quantitate. Tribromoacetaldehyde had fast decay. 

Both carbon tetrachloride and benzyl chloride had slow decays. 

According to the plots of concentration vs. time (Figure 8), it appeared as if the following 
DBPs were highly unstable in the presence of ascorbic acid at pH 3.5: bromodichloro-, 
dibromochloro-, and tribromoacetonitrile, and bromodichloro-, dibromochloro-, and 
tribromonitromethane. Previous research has shown that trichloroacetonitrile can undergo base- 
catalyzed hydrolysis, but it is stable at acidic pH. The brominated versions of some of these 
DBPs (i.e., tribromoacetonitrile, bromodichloroacetonitrile, and dibromochloroacetonitrile) may 
be even more unstable and may break down in the presence of ascorbic acid. However, 
tribromonitromethane was stable at pH 4 in the presence of ammonium chloride, so it was 
possible that heavy, brominated DBPs may be stable in the presence of ammonium chloride at 
pH 3.5. 


THMs - 
Iodo-THMs - 
Haloacetonitriles - 


Chloropropanones - 
Bromopropanones - 
Halonitromethanes - 


Haloacetaldehydes - 
Miscellaneous - 


A new holding study was carried out to evaluate ammonium chloride as a quenching 
agent/preservative at pH 3.5. Ascorbic acid at pH 3.5 was tested in parallel on DBPs of interest 
(e.g., bromodichloro-, dibromochloro-, and tribromoacetonitrile, and bromodichloro-, 
dibromochloro-, and tribromonitromethane). The hypothesis was confirmed, and additional 
sample bottles containing ammonium chloride quenching agent/preservative were added for the 
LLE-GC-ECD method. These six compounds were dropped from the SPE method because of 
the additional work load that would have been involved in sampling and extraction. 


358 


70 


60 


50 


= 40 



o 

o 


20 


10 


0 



0 3 6 9 12 15 18 21 


-B-CAN-WI 
—CAN-WE 
—0—BAN-WI 
BAN-WE 
—A—DCAN-WI 
—A—DCAN-WE 
—X—BCAN-WI 
—3K—BCAN-WE 

-DBAN-WI 

-DBAN-WE 

—e—TCAN-WI 
—I—TCAN-WE 
•HB—BDCAN-WI 
—BDCAN-WE 
DBCAN-WI 
—«~DBCAN-WE 
—Ar-TBAN-WI 
—A—TBAN-WE 


Day 


Figure 8. Ascorbic acid/pH 3.5 holding study results for haloacetonitriles (Weymouth 
filtration plant influent and effluent). 


Migration to Saturn Ion Trap Mass Spectrometer 

The SPE method was implemented on the ion trap mass spectrometer as a backup system 
in the event that the TS-250 mass spectrometer would become unusable for the project. If, at the 
end of this additional methods development period, the ion trap results were much better, then 
the SPE method would be permanently migrated to the Saturn 2000 ion trap mass spectrometer 
for all subsequent work. Restrictions to this work included: a) not using MtBE as the extraction 
solvent, and b) keeping the instrument as "stock" as possible for easy switch-over to purge-and- 
trap operation. Most of the initial testing occurred during late June 2001, when the performance 
of the existing DB-624 GC column and alternative solvents were tested. It was found that unless 
the original procedure was kept intact, from development with the TS-250 mass spectrometer, it 
would be difficult to achieve similar results. From previous work comparing different GC 
columns, a switch to the preferred DB-1 column was necessary. Because of the extra efforts 
involved in switching columns frequently, it was hoped that the DB-1 column could be used for 
both SPE and P&T analysis on the same instrument. Initial work would include optimizing some 
instrumental parameters, automating the system, running full calibration curves (0.5 - 30 pg/L), 
and injecting a suite of samples to establish a preliminary MDL. The results of this SPE work on 
the ion trap mass spectrometer showed that low-level detection was possible for almost all of the 
compounds that were part of the original SPE technique performed on the TS-250 instrument. 


359 















































Results for chloroform, dichloroacetaldehyde, chloroacetonitrile, and chloropropanone 
could not be obtained because they co-eluted with the hexane solvent that was now part of the 
solvent extraction system. Of the solvents listed below, /7-hexane was a logical choice based on 
the boiling point of the solvents. If the solvent is too volatile, the extraction process would 
become more difficult because SPE extractions occur under vacuum. Unfortunately, hexane is 
very non-polar and does not remove as many DBPs from the Bond Elut sorbent material. A 
mixed solvent system of 50:50 hexane/methylene chloride allowed full extraction of the DBPs, 
and, at the same time, avoided bringing MtBE and larger amounts of MeCb into the VOC room, 
where they are routinely determined as part of the VOC method (Table 4). 


Solvents* 

Boiling Point f°C) 

Comments 

Ethyl ether 

34.6 


Pentane 

36.1 


Methylene chloride 

39.8 

VOC compound 

Carbon disulfide 

46.5 


Methyl tert -butyl ether 

55.2 

VOC compound 

Chloroform 

61.2 

VOC compound 

/7-Hexane 

69.0 


Benzene 

80.1 

VOC compound 

Cyclohexane 

80.7 


Iso-octane 

99.3 


Toluene 

110 

VOC compound 


* Recommended for non-polar columns (100% methyl or 5% phenyl, 95% methyl) 


Compound Notes 

Dichloroacetonitrile had a co-elution problem with an unknown impurity that seemed to 
be present in the standards. The co-elution also occurred when MtBE was used as the extraction 
solvent on the TS-250 instrument, but there was not sufficient resolution to resolve the co-eluting 
peak from dichloroacetonitrile, and the two peaks were integrated together to produce a 
systematic error. 

Bromonitromethane was a minor problem for quantitation because it eluted between 
dibromochloromethane and bromochloroacetonitrile, both of which have small m/z 93 
contributions to bromonitromethane’s main quantitation mass channel. On the TS-250 
instrument, this problem could be solved by manually re-integrating the peaks. 

Chloronitromethane and bromochloracetaldehyde were eliminated from the SPE method 
because of their co-elution on the DB-1 column with chloral hydrate (TCA) and each other. 


360 





Table 4. Varian Saturn 2000 performance with 1:1 Hexane/MeCh solvent system and 
updated GC program. Shaded compounds were later removed from the SPE method. 


Compound 

Saturn 2000 Retention Time 

Quantitation 

Confirmation 

Lowest Standard Estimate 


Usinq Updated GC Program 

m/z 

m/z 

(Ion Trap. DB-1. Splitless) 

Chloroform 

Blocked by solvent 

83 

49 

Blocked by solvent 

Dichloroacetaldehyde 

Blocked by solvent 

49 

83 

Blocked by solvent 

Chloroacetonitrile 

Blocked by solvent 

75 

77 

Blocked by solvent 

Chloropropanone 

Blocked by solvent 

43 

49 

Blocked by solvent 

Carbon Tetrachloride 

9 40 mm 

117 

49 

0 50 ppb 

frichloroacetonitrile 

9 69 min 

108 

49 

0 50 ppb 

Dichloroacetonitnle 

10 78 mm 

74 

49 

0 75 ppb 

Bromodichloromethane 

11 15 min. 

83 

79 

0 75 ppb 

Chloronltromethane 

Co-elution Problem 

49 

N/A 

Co-elution Problem 

Bromochloroacetaldehyde 

Co-eluhon Problem 

130 

N/A 

Co-elution Problem 

1.1 -Dichloropropanone 

13 19 min 

43 

93 

1 0 ppb 

Dichloromtromethane 

13 95 min 

83 

48 

2 5 ppb 

Bromoacetonitnle 

14 91 min. 

119 

79 

? 

Chloropicnn 

20 14 mm. 

117 

49 

1.0 ppb 

Bromodi chloroacetonitrile 

20 18 min 

108 

154 

1.0 ppb 

Dlbromochloromethane 

20 94 min. 

127 

208 

0.50 ppb 

Bromomtromethane 

21.29 min. 

93 

79 

? 

Bromochloroacetomtrile 

21 64 min. 

74 

155 

0 50 ppb 

Dichloroiodomethane 

25 08 min. 

83 

127 

7 

Bromochloronitromethane 

26 62 min 

129 

79 

0 75 ppb 

1,1.1-Tnchloropropanone 

28 66 min 

43 

83 

1 0 ppb 

1,3-Dlchloropropanone 

30 08 mm 

77 

49 

1 Oppb 

Bromoform 

31 80 min. 

173 

254 

0.50 ppb 

Di bromoacetonitnle 

32 58 min. 

118 

79 

0.50 ppb 

Bromodichloronitromethane 

32 61 min 

163 

49 

0 50 ppb 

Dibromochloroacetonitnle 

33 05 min. 

154 

74 

0 50 ppb 

1.1-Dibromopropanone 

33 66 min. 

43 

173 

1 0 ppb 

Bromochloroiodomethane 

33 90 min 

127 

175 

0 50 ppb 

Dibromonitromethane 

34 68 min 

173 

43 

0 75 ppb 

1-Bromo-1,1-dichloropropanone 

36.28 min. 

43 

127 

2 5 ppb 

1.1,3-Tnchloropropanone 

37.07 min. 

77 

83 

0 75 ppb 

Tribromochloromethane 

37 89 min. 

207 

79 

0 75 ppb 

DI bromochloronitromethane 

39 76 min. 

207 

79 

7 

Di bromol odomethane 

39 99 mm. 

127 

173 

0 75 ppb 

Tribromo acetaldehyde 

40 24 min 

251 

N/A 

7 

Tnbromoacetomtnle 

40 39 min. 

198 

79 

0 75 ppb 

Benzyl chlonde 

41 09 min. 

91 

126 

0 50 ppb 

Chlorodiiodomethane 

41 44 min. 

175 

127 

0 50 ppb 

1,1,3,3-T etrachloropropanone 

41 88 min. 

83 

111 

2 5 ppb 

1.1.1,3-Tetrachloropropanone 

42 10 min. 

77 

49 

0 50 ppb 

Bromopicnn 

43 64 min 

251 

172 

2 5 ppb 

C8-CI Internal Standard 

44 40 min. 

91 

N/A 

N/A 

Bromodi i odomethane 

46 23 min. 

219 

127 

0 50 ppb 

1,1.1 -Tn bromopropanone 

46 77 mm. 

43 

251 

7 

1.1,3-Tribromopropanone 

49 89 min. 

121 

93 

1 0 ppb 

Iodoform 

50 69 min. 

127 

267 

0 50 ppb 

1.1.3.3-Tetrabromopropanone 

53 06 min 

120 

173 

7 


1,1,1,3-Tetrachloropropanone showed an unrecoverable co-elution with an impurity late 
in the chromatographic run (retention time of 42.1 min.). There was no solution to this problem, 
so poor quality assurance (QA) data was obtained for this compound, following migration to this 
method. 


1,1,3,3-Tetrabromopropanone (retention time of 53.1 min.) exhibited poor quantitation 
for standards and was the latest eluting compound of all the DBPs studied. Either 1,1,3,3- 
tetrabrompropanone was slowly degrading or quantitation of this compound was made difficult 
because of poor signal-to-noise in this section of the chromatographic run, when the GC oven 
was doing its final ramp to 301 °C. The baseline rises significantly about 52 min into the run. 

Multiple Quantitation Ions 

The main obstacle for quantitation of SPE results was low signal-to-noise of the 
chromatographic peaks. The electron capture detector is inherently more sensitive for detection 
for halogenated compounds (as low as 0.10 ppb). SPE and P&T are comparable for minimum 
reporting levels, generally 0.20 to 0.25 ppb. The peaks are often much sharper and more distinct 
using P&T because of a lack of solvent and full injection of the sample aliquot. 

A new strategy of using multiple quantitation ions for improving SPE sensitivity was 
tested. In the past, the SPE method used the most optimum ion channel for high abundance and 


361 
























































































minimal interference problems from other peaks. In this new strategy, the original quantitation 
ion was added to the next-largest ion that was a significant contribution to the El mass spectrum. 
This provided up to a two-fold improvement for some compounds. About one-third of the 
compounds showed improvement, with a previous reporting level of 1.0 pg/L now becoming 
0.50 pg/L. 

MDL and Sample Reporting 

All of the remaining 35 compounds gave results comparable to or better than those 
obtained in the past using the TS-250 instrument. In several cases, the lowest calibration 
standards could be dropped to 0.25 pg/L. (In previous work, the lowest calibration point was 1 
pg/L, and a reasonable MDL was established at 3 pg/L). 

The ten calibration standards for the Varian ion trap were at concentrations of 0.25, 0.50, 
1.0, 2.5, 5.0, 7.5, 10, 15, 20, and 30 pg/L. After calibration curves had been established, the data 
files for 0.25 pg/L - 5.0 pg/L standards were duplicated and processed as if they were actual 
samples to check the accuracy and integrity of the calibration curves. Table 5 shows these 
results. If the reported values were within 30% of the theoretical values, then the results were 
designated in bold type, and the lowest, reliable values to report are shown in a shaded highlight. 
As an example, the results for a recent Alameda County Water District sampling on 3/19/02 
showed that the values used for SPE results reporting could be set much lower than those 
produced from a simple MDL comparison (Table 5). Because this was such an important survey 
study, and real world results are often below 5 pg/L for any given DBP, it was necessary to 
extract all available information that we could from this SPE method. 

Success with Migration of SPE Technique to Ion Trap 

The SPE technique was successfully implemented on the Saturn 2000 ion trap mass 
spectrometer. Full-scan mode on the Saturn ion trap provided more mass spectral information 
and improved the sensitivity over the TS-250 instrument. The ion trap mass spectrometer 
provided full automation and overnight runs, along with more reliable operation. Because both 
the SPE and P&T methods used the same instrument for analysis, comparison of results was 
much better. Because of these advantages, the Saturn 2000 ion trap mass spectrometer was used 
for all subsequent samplings. 

Comparison of SPE to P&T and LLE 

The pursuit of multiple analytical techniques for the Nationwide DBP Occurrence Study 
led to a complementary scheme for data analysis and interpretation — the liquid-liquid extraction 
technique would be the primary method used for quantitation, and other techniques such as P&T, 
SPE, or SPME could provide true confirmation of a compound's presence. Not all the techniques 
could analyze for each compound. Table 6 shows the comparison of results using SPE, P&T, 
and LLE techniques. The results were very consistent. Because this is only a comparison of 


362 


how SPE results compare to the other techniques, many of the compounds that were part of this 
study, but were not amenable to SPE, were intentionally left off the table. 

Table 5. Minimum reporting levels (MRLs) for Alameda County Water District sampled 
on 3/19/02. A concentration in bold represents values that lie within the + 30% range. 
Shading represents the lowest reportable level for this study set. 


Compound 

Quantitation 

0.25 ug/L 

0.50 ug/L 

1.0 ug/L 

2.5 ug/L 

5.0 ug/L 

Minimum Reporting 

MDL Comparison 


Ions 

(0 175- 0 325) 
Range 

(0 350*0 650) 
Range 

(0 700* 1.300) 
Range 

(1.750* 3.250) 
Range 

(3.500-6.500) 

Range 

Level 


Halomethanes 









BDCM 

83+05 


0.701 

0.835 

2.355 

4.034 

1.0 ppb 

4 ppb 

DBCM 

127+129 

0.229 

0.643 

0.860 

2.488 

3.910 

0.25 ppb 

6 ppb 

TBM 

171+173 


0665 

0.953 

2.659 

4.221 

1.0 ppb 

5 ppb 

TBCM 

207+209 

0.219 

0.476 

0.818 

2.119 

7.445 

0.25 ppb 

5 ppb 

DCIM 

83+05 

0.250 

0.534 

0.845 

2.417 

4.406 

0.25 ppb 

4 ppb 

BCIM 

127+129 

0.253 

0.665 

0.842 

2.316 

4.068 

0.25 ppb 

4 ppb 

DBIM 

127+173 



0.774 

2.244 

4.424 

10 ppb 

3 ppb 

CDIM 

127+175 


0.481 

0.701 

2.381 

4.516 

0.50 ppb 

4 ppb 

BDIM 

219+221 




1.990 

5.899 

2.5 ppb 

4 ppb 

TIM 

127+267 




1.968 

4.014 

2 5 ppb 

4 ppb 

Haloacetonitriles 









BAN 

119+121 



1.027 

2.450 

8.820 

1 0 ppb 

12 ppb 

DCAN 

74 


1.095 

0 539 

2.876 

3.317 

2.5 ppb 

6 ppb 

BCAN 

74+76 


0.592 

0.842 

2.461 

3.963 

0.50 ppb 

5 ppb 

DBAN 

118+120 


0.544 

0697 

2.370 

3.798 

0.50 ppb 

4 ppb 

TCAN 

108+110 


0.537 

0.793 

2.341 

3.708 

0.50 ppb 

3 ppb 

Haloketones 









1.1-DCP 

43+63+03 




2.935 

3 351 

2.5 ppb 

5 ppb 

1,3-DCP 

77+79 




2.014 

4.154 

2.5 ppb 

5 ppb 

1.1 -DBP 

43+79+173 


0888 

1.012 

2.334 

4.229 

1.0 ppb 

5 ppb 

1,1,1-TCP 

43+97+125 


0.595 

1.031 

2.961 

4.024 

0.50 ppb 

4 ppb 

1.1.3-TCP 

77+03 




2.441 

3.504 

2.5 ppb 

7 ppb 

1,1.1-BDCP 

43+97+125 



1.119 

2.949 

3.953 

1.0 ppb 

4 ppb 

1.1,1-TBP 

1,1,3-TBP 

43+79+251 

121+123 




1.989 

4.235 

3.848 

2.5 ppb 

5 0 ppb 

9 ppb 

11 ppb 

1.1,3,3-TeCP 

83+85 




1.830 

3.505 

2.5 ppb 

8 ppb 

1.1,1,3-TeCP 

77+79 






» 5 ppb 

12 ppb 

1.1.3.3-TeBP 

120+122 






» 5 ppb 

8 ppb 

Haloacetaldehyde 









TBA 

172+173 




2.543 

6.380 

2.5 ppb 

8 ppb 

Halonitromethanes 









BNM 

95 





5.092 

5.0 ppb 

10 ppb 

DCNM 

BCNM 

83+85 

127+129 

0 401 

0.678 

1.083 

2.111 

3.778 

4.220 

1.0 ppb 

5 0 ppb 

10 ppb 

8 ppb 

DBNM 

171+173 


0.640 

1.039 

2.250 

3.999 

0.50 ppb 

7 ppb 

TCNM 

117+119 


0.509 

0.923 

2.473 

4.095 

0 50 ppb 

4 ppb 

Misc. Compounds 









CT 

117+119 



1.035 

1.978 

6.515 

1.0 ppb 

4 ppb 

BC 

91+126 

0.192 

0.552 

0.841 

2.138 

7.011 

0.25 ppb 

4 ppb 

1.1.2.2-TeBCE 

141+299 




1.463 

5.821 

5.0 ppb 

Not Available 


363 





























































































Table 6. Comparison of results for SPE, P&T, and LLE analysis for Alameda County 
Water District. Patterned boxes denote that the compound was not reported for that 
method. 


Alameda 

County 

Water 

District 

3/19/02 


UJ 

JX 

ii 

n -> 
© <£ 
£ 5. 


5 

If 

£ % 
u. & 


< 

£ 


o 

SP 

It 

to ^ 

Q £ 


5 9 

£ 

o *z 


Ha kxnelhanes 

BromodicKtororwthijne 
Otwomochk* ocrwrtfcane 
Bromoform 

Trl>fomochk>fo#wt*ian€ 

Bro*rocti^o»o<Jorneinarie 

D^fonv^fodonv/thane 

CWorcxJixxJometharxr 

Bfcmoditodomclharw 

Iodoform 


5 P* 

J&L. 


pit 


»« 


S»« 

stft 


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JP* 






*3 

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ft-'* 


tf.iz 


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<9?r, «*? ft-A- 


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gft* HM* 

$t? nrA* 


i# 


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210 




20? 59? 

OA* *2 

# A«*l 


IOfe 13ft 

«»>*! 


<5 


Hafe»*c«U>ttitHf«s 
Brooioacotowlrilc 
Dk hioroacetonitr ile 
Br o^KJcWoroat <Ho<yfnJc 
Dtbroovoaccfonrtrilc 
Tochlo-roacftlocitrik? 


i* 

#vo 

65* 


Halt>k*?or»*i 

1.1- DcMofopioparvooc 
1 3-D*chkxopropanorve 

1.1 -Cvt# ofTKjpropanorvo 

1.1.1 -Trichlor opr opanooc 

1.1.3- Tj icbkxoprofKmone 

11.1- Bromwtehteopr ©paoor* 

1.1.1 *Tr ibcomop<op»nofW! 

1.1.3- Trihfomofxopanooe 

1 1A>Totra<hk^<>proprvx»nc 

1.1.1 .3- T ctrachloropr opanono 
1,1.3>Tfettabromopf opar>on» 


(09*j i » 


1 i 




1 IV 


I* 


<$??) «.tt 


J94*| 29 


JM »« 


2.01 5?* SO 


HaloacpJald^ydw, 

Trtbfomoacetokkyh)^ 




1«$ J«2 45 


Halooifromethanes 

Br omooaromerhane 
DKhloron^romeihanc 
Br omoc h»orofWt< on>?thar>e 
DAtomorvtromctNi/ie 
T rtchter orvrtf omolhaoc 







181 


Wise Compounds 

Carbon tcttacWond* 

Benzyl Chloride 
1.1.2 2-TotrabromochlcrocthaT* 



* CompCMmd is present but could not be quantitated 
‘ Higih sjxkn mcovMy 


CONCLUSIONS 

There was no one universal method that could be used to analyze all targeted DBPs. 
LLE-GC-ECD is the most universal of all the techniques, but it does not provide the definitive 
results that a mass spectrometric technique provides. Of the two mass spectrometry techniques 
examined (P&T-GC/MS and SPE-GC/MS), P&T-GC/MS excelled at measuring volatiles and 
benefited from being a solvent-less technique. SPE, on the other hand, can make use of a variety 
of sorbents to target specific families of compounds or to provide general screening results, as 
was the case for this study. 

The solid phase extraction technique was developed to incorporate as many compounds 
as possible. To this end, we achieved our goal. In future work, we hope to improve upon the 
technique by taking advantage of many new sorbents that have appeared on the market, which 
offer improved extraction efficiencies that should provide lower detection limits. We are also 
pursuing an on-line solid phase extraction apparatus that will remove the need for an operator to 
extract the cartridges by hand, which should improve reproducibility. A fully automated on-line 
SPE system would offer the flexibility to screen many compounds, ranging from volatiles to 
semi-volatiles, with full mass spectrometric detection and limited user intervention. 


364 
























































LIQUID-LIQUID EXTRACTION-GAS CHROMATOGRAPHY- 
ELECTRON CAPTURE DETECTION METHOD 


INTRODUCTION 

Different versions of the gas chromatographic (GC) method were used during the course 
of this disinfection by-product (DBP) occurrence project since the method was still undergoing 
major development during the utility sampling phase. A short description of the final version of 
the method will be given, followed by a history highlighting some of the major changes that 
occurred during the method development. The method changes improved the scope and quality 
of the method over the development period. 

METHOD SUMMARY 

The basic method used GC with a salted liquid-liquid extraction (LLE) procedure to 
quantitate and confirm 47 drinking water DBPs (Figure 1). For this method, two different GC 
columns were operated simultaneously (DB-1 and DB-5), which permitted the separation and 
quantitation for all of the analytes. The method included two different internal standards used as 
reference peaks. Samples were collected in two analytical fractions; however each fraction used 
the same sample preparation method. The two analytical fractions were used to accommodate 
the use of two different chemical preservatives (ascorbic acid and ammonium chloride). The 
method required two separate extractions and two GC injections of each sample to achieve the 
quantitation for all 47 DBPs. Sample preparation included collection of a 30 mL volume of 
sample, salting with 11 g of sodium sulfate and 1 g of copper sulfate, and extraction with 3 mL 
of methyl tertiary -butyl ether (MtBE). A mechanical platform shaker was used for automated 
sample extraction. The copper sulfate enhanced analyte recovery and aided in the extract 
transfer process. An autosampler injected sample extracts onto a split-splitless GC injection 
port, and a two-channel data system simultaneously collected the two chromatograms for each 
injection. 


365 


Water sample 
20 ml 


<=^ 





Add 2 mL MtBE w/internal standard 
(1,2-dibromopropane) 

Add 1/2 g copper 
sulfate 

Add 8 g sodium 
sulfate 


Mechanical Shake for 5 minutes 



Let stand for 5 minutes 


Transfer ca. 1/2 ml to autosampler vial 


GC/ECD 


Figure 1. Summary of the LLE-GC-ECD method. 


Sample Preparation 

A 30 mL glass syringe was used to transfer samples into 40 mL glass vials. Daily 
procedural calibration standards were prepared with each set of samples using acidified reagent 
water. Sample matrix spikes and sample duplicates were prepared with each sample set. The 
MtBE extraction solvent contained two different internal standards. Because the MtBE was 
prepared with the internal standard, additional steps of adding the internal standard to each 
sample extract was eliminated. After 3 mL of MtBE was added, 11 g of dried sodium sulfate and 
1 g of copper sulfate were added. The sample was capped and shaken briefly by hand before 
placing into a sample holder. After the solvent and salt were added to all of the samples, they 
were shaken using a vortex mixer for 11 min. A disposable Pasteur pipette was used to transfer 
approximately 2 mL of extract evenly between the two autosampler vials. One vial was stored in 
a freezer as a backup extract, and the other vial was was used for analysis. 


366 





















Gas Chromatography Method 

This GC method accomplished the separation and quantitation of 47 drinking water 
DBPs. The method involved the simultaneous analysis of one sample injection on two different 
analytical columns. The two different columns were attached to one injection port, allowing 
each sample to be analyzed by a GC equipped with two electron capture detectors (ECD). The 
two channels of data were collected simultaneously and processed sequentially. Unlike previous 
GC methods where one column is used as the primary analytical column for quantitation and a 
secondary column is used as a confirmation column, this method used both columns as primary 
analytical columns, with each column also used for confirmatory analysis. Using two different 
analytical columns allowed coeluting peaks to be resolved. 

Two sets of samples collected from the each location because two different sample 
preservatives were required. Forty-one compounds were preserved and collected using ascorbic 
acid (AA). Ammonium chloride (AC) was used to preserve six other compounds (tri- 
halonitromethanes) that could not be preserved using ascorbic acid. Both the ammonium 
chloride and the ascorbic acid fractions were analyzed using the dual primary column analysis 
method. When analyzing the ascorbic acid fraction, one column could separate 25 compounds, 
and the other column could separate the other 16 compounds. Some compounds could be 
resolved on both columns, while other compounds could be resolved only on one of the columns. 
When a compound was separated on both columns, one column was used as the primary 
quantitation column, and the other column used for confirmation. Table 1 lists which DBPs 
coelute for each column. Ascorbic acid was used as a preservative for all sampling locations. 
Later in the study, ammonium chloride was used as a preservative for a smaller subset of those 
same sampling locations 

When ammonium chloride-preserved samples were analyzed using the dual primary 
column analysis, 4 compounds could be resolved on one column, and the other two on the other 
column. Both columns were used for confirmation, as described for ascorbic acid-preserved 
samples. Ammonium chloride-preserved samples were extracted and analyzed using the same 
LLE procedure and GC conditions as for ascorbic acid-preserved samples. 

Four separate GC software methods were developed to allow all 47 compounds to be 
analyzed. The 47 compounds were analyzed by producing four different chromatograms and 
calibrating most of the compounds twice. Data processing was done in pairs for each analytical 
fraction to enable cross-checking between columns. This aided in the analyte identification and 
detection process. 

The primary column “A” was a DB-1 (J & W Scientific/Agilent, Folsom , CA, 30-m, 
0.25- mm ID, 1-pm film thickness); primary column “B” was a DB-5 (J & W Scientific/Agilent, 
Folsom, CA, 30-m, 0.25-mm ID, 1-pm film thickness). Both analytical columns were installed 
onto a single GC injector (Model 3600, Varian Analytical Instruments, Walnut Creek, CA). The 
GC was equipped with two ECDs and an autosampler (Varian Analytical Instruments, Walnut 
Creek, CA). The autosampler injected 4.7 pL of extract onto a Model 1077 split-splitless 
injector operated in the splitless mode. The “A” and “B” channel ECD outputs were connected 
to a PE Nelson 970 interface (Perkin Elmer Corp., San Jose, CA). 


367 


Table 1. Gas chromatographic interferences for disinfection by-product analysis 3 



DB-1 (10 coelutions) 

DB-5 (14 coelutions) 




1 

cnm+bca+tca 

can+tcan 

2 

tcnm+bdcan 

Cnm+11 dcp 

3 

1133tecp+13dbp 

Bnm+bcan 

4 

dban+bdcnm 

113tcp+tbcm 

5 

(ban+i) A 

tba+dbim 

6 


bc+tban 

7 


1133tecp+cdim 


A ban appears to coelute with an interference peak 





Shouldered Peaks* 

Shouldered Peaks 

1 

bnm & bean & i 

tea & dean 

2 

13dcp & i 

1 ldbp & dban & bcim 

3 

tbm & i 

Bdim & i 

4 

bcim & 1 ldbp 


5 

dbim & i 


6 

111 tbp & i 






*i=unknown interference 



a Compound Abbreviations are Shown in Table 3 


The GC operating conditions shown in Table 2 were optimized to enhance sensitivity. A 
low injection temperature of 87 °C was used to minimize degradation of thermally labile 
compounds. A large injection volume of 4.7 pL was chosen to increase sensitivity. Column 
flow rates and other conditions were adjusted to maximize resolution and detection for each 
compound. 


368 

























Table 2. Gas chromatograph operating conditions 














GC Temperature Program: 











Temperature (°C): 

35 


139 


301 






Rate (°C/minutek 


4 


27 







Time (minutes'): 

23 


0 


5 

















Flow rates: 

Helium carrier gas at 35°C 

DB-1 Column = 2.3 ml/min 








DB-5 Column = 1.3 ml/min 





Head Pressure 14.3 

psi 





















Rear Injector Varian model 1077 capillary snlit/solitless 







Split ratio - 12 











Iniector temperature = 87 °C 









Injection mode splitless 










Split valve program 0.89 min (relav=2) 



















Detector Varian Nickel 63 Electron Capture Detector (ECD) 






Two regular size ECD’s (model # 02-001972-OC 

)) 






Operating Temperature = 297 °C 









Make-up gas Nitrogen at 29.3 mL/min 








Autozero on 












Range 10 























Varian model 8200 Autosampler 










Injection Volume = 4.7 uL 










Solvent plug size= 0.1 uL 










Slow injection rate= 2.3 uL/sec 









Upper air gap and lower air gap selected 







Viscosity = 4 











Resevoir pressure= 27psi 










Resevoir solvent= MtBE 





















Other Parameters 












Thermal stabilize time=1.07 min 









Column standby temperature^ 117 °C 








Column A and B installed: 

A=J&W DB-1. 30 meter, 0.25 mm I.D., 1 micron film thickness 





B=J&W DB-5. 30 

meter. 0.25 mm I.D.. 1 micron film thickness 


GC= Varian model 3600 










A central laboratory gas manifold svstem sunnlies nitrogen and helium gas 



Dual channel data aquisition 1 volt input to model 970 PE Nelson Interface/Buffer 



Chromatoeranhv Software PE Turbochrome Navisator (ver4.H 1987-1995 



369 







































































































Calibration and Data Processing 

Two sets of calibration standards were prepared from five different intermediate stock 
solutions (Table 3). The ascorbic acid spiking solutions contained the first 41 compounds (Table 3), 
and used 7 different concentration points (over the range of 0.1 - 80 pg/L) for the calibration curve. 
An additional high concentration point was added for THM analyses to enable the concentration 
range to extend to 120 pg/L (ppb). Ammonium chloride spiking solutions contained 6 compounds 
(trihalonitromethanes) (Table 3), and used 7 different concentration points (over the range of 0.5 - 20 
pg/L) for the calibration curve. Calibration standards were prepared daily from stock solutions. 
Standards and blanks were prepared in pH-adjusted, distilled water (adjusted to 3.5 with concentrated 
sulfuric acid). Direct standards (non-extracted standards) were also prepared with each daily batch of 
extractions. Individual stock solutions were prepared on an annual basis, intermediate stock 
solutions were prepared quarterly, and spiking solutions were prepared bimonthly. All sample 
extracts and standard solutions were stored in the freezer at -11 °C. 

Method Development Highlights 

A short chronology of the major steps in the method development will be discussed. Each 
step is included because it has affected the type and quality of the project data. The variations in 
methods used over the project period can help to identify differences in the data over the utility 
sampling period. 

The GC method development started in December 1998 and continued through the end of the 
utility sampling phase (April 2002). From February 1999 to August 2000, initial GC-ECD, purge- 
and-trap-GC/MS, and solid phase microextraction (SPME)-GC/MS methods were developed. In 
October 2000, due to operational problems with the Varian 3500A GC, two other GCs (a Varian 
3500B and a Varian 3600) were configured for the dual column-GC-ECD analyses. Between 
February and March 2001, adjustments were made to the GC temperature program to achieve better 
separations. Higher quality-control spike concentrations of THM standards (50 ppb) were also made 
during this time. In March 2001, 9 additional compounds were added to the GC method 
(dichloronitromethane, bromochloronitromethane, tribromonitromethane, 1,1-dibromopropanone, 1- 
bromo-l,l-dichloropropanone, 1,1,1-tribromopropanone, 1,1,3-tribromopropanone, 1,1,1,3- 
tetrachloropropanone, and bromodichloroacetonitrile). Between May and July 2001, the extraction 
method was improved to increase the concentration factor and improve analyte recoveries. At this 
point, ammonium chloride was also introduced as a second preservation chemical, and the remaining 
4 analytes were added to the method (tetrabromochloroethane, dibromochloronitromethane, 
bromodichloronitromethane, and chloronitromethane), for a total of 47 analytes. An additional 
internal standard (2-bromo-l-chloropropane) was also added to aid in analyte identification. 

Table 4 shows the improved recoveries that were accomplished by the adjustments in the 
LLE-GC-ECD method. Table 5 shows the method reporting limits (MRLs) for the LLE-GC-ECD 
method compared to the SPE-GC/MS and P&T-GC/MS methods. In general the LLE-GC-ECD 
method reporting limits were the same or lower than other methods (Table 5). 


370 


Table 3. Stock standard calibration preparation 




Compounds 


Stk 

Stk 

Chk 

Purity 

Adj 

uL in 

cone 

btl 

# 



Date 

ppm 

Date 


cone 

lmLACN 

ppm 

A 

1 

1 

lOOppm THM & 551B mix 

chloroform 

tcm 

11/28 

2000 


99+ 

2000 

50 

100.0 

2 

2 

bromodichloromethane 

bdcm 


Supelco 



ppm 



3 

3 

chlorodibromomethane 

cdbm 


4-8140u 






4 

4 

bromoform 

tbm 


MeOH 






1 

5 

Dichloroacetonitrile 

dean 

11/28 

2000 


99+ 

2000 

50 

100.0 

2 

6 

bromochloroacetonitrile 

bean 


Supelco 



ppm 



3 

7 

dibromoacetonitrile 

dban 


4-8046 






4 

8 

trichloroacetonitrile 

tcan 


acetone 






5 

9 

1,1 -dichloropropanone 

1.1-dep 


551b 






6 

10 

1.1.1 -trichloropropanone 

1.1.1 -tep 


dbp 






7 

11 

chloropicrin 

tenm 


mix 






1 

12 

1,1,2,2-tetrabromo-1 -chloroethane 

tebce 

9/28 

3700 

6/29 

78.7 

2912 

35 

101.9 

B 

1 

13 

lOOppm Halomethane mix 

Bromochloroiodomethane 

bcim 

4/6 

3400 

5/16 

96.4% 

3300 

32.0 

105.6 

2 

14 

Dichloroiodomethane 

dcim 

4/6 

2100 

5/16 

90.2% 

1900 

54.0 

102.6 

3 

15 

Dibromoiodomethane 

dbim 

4/6 

3500 

5/16 

99.0% 

3500 

28.6 

100.0 

4 

16 

Chlorodi iodomethane 

edim 

4/6 

3900 

5/17 

68.3% 

2650 

38.0 

100.7 

5 

17 

Bromodi iodomethane 

bdim 

4/6 

4800 

5/16 

93.8% 

4500 

23.0 

103.5 

6 

18 

Iodoform 

tim 

4/5 

6900 

5/17 

99.0% 

6900 

15.0 

103.5 

7 

19 

Tribromochloromethane 

tbcm 

4/6 

4200 

5/16 

94.9% 

4000 

26.0 

104.0 

C 

1 

20 

lOOppm Halo(acetonitrile & ac 

Bromoacetonitrile 

italdehyd 

ban 

2 ) mix 

9/28 

4400 

5/10 

99+% 

4400 

23.0 

101.2 

2 

21 

Chloroacetonitrile 

can 

4/5 

2000 

5/10 

99+% 

2000 

50.0 

100.0 

3 

22 

Dichloroacetaldehvde 

dca 

4/6 

4600 

5/14 

99.0% 

4600 

24.0 

110.4 

4 

23 

Bromochloroacetaldehyde 

bca 

7/17 

2400 

7/19 

54.1% 

1298 

78.0 

101.3 

5 

24 

Tribromoacetaldehyde 

tba 

4/6 

3200 

5/14 

99.0% 

3200 

32.0 

102.4 

6 

25 

chloral 

tea 

9/23 

1000 


99+% 

1000 

100.0 

100.0 

D 

1 

26 

lOOppm Haloketone mix 

Chloropropanone 

cp 

4/10 

2100 

5/14 

98.0% 

2050 

50.0 

102.5 

2 

27 

1,3-Dichloropropanone 

1.3-dcp 

4/5 

6500 

5/14 

99.0% 

6500 

15.4 

100.1 

3 

28 

1.1,3-Trichlorot>rot>anone 

1.1.3-tcp 

4/5 

1900 

5/15 

99.6% 

1900 

54.0 

102.6 

4 

29 

1.1,3.3-Tetrachloropropanone 

1,1,3,3-teep 

4/6 

2000 

5/15 

99.0% 

2400 

42.0 

100.8 

5 

30 

1.1.1,3-TetrachloronroDanone 

1.1,1,3-tecp 

4/6 

2200 

5/15 

92.4% 

2050 

50.0 

102.5 

6 

31 

1 -Bromo 1.1 dichloropropanone 

1-b 1,1 dep 

4/6 

2700 

5/15 

77.6% 

2100 

50.0 

105.0 

7 

32 

1.1 -DibromoDroDanone 

1.1-dbp 

6/29 

1800 

5/15 

94.0% 

1700 

60.0 

102.0 

8 

33 

1.1.1 -Tribromopropanone 

1.1.1 -tbt> 

4/6 

2600 

5/15 

97.0% 

2500 

40.0 

100.0 

9 

34 

1.1,3-TribromoDroDanone 

1.1,3-tbn 

6/29 

2200 

5/15 

97.6% 

2150 

48.0 

103.2 

10 

35 

1,1,3,3-Tetrabromopropanone 

1,1,3,3-tebp 

4/6 

6400 

5/15 

99.0% 

2000 

50.0 

100.0 

E 

1 

36 

lOOppm Halonitromethanes +1 

Chloronitromethane 

c mix 

enm 

9/28 

5300 

5/14 

99.0% 

5300 

19.0 

100.7 

2 

37 

Bromonitromethane 

bnm 

4/5 

3100 

5/14 

99.0% 

3100 

34.0 

105.4 

3 

38 

Dichloronitromethane 

denm 

4/5 

2900 

5/14 

99.0% 

2900 

36.0 

104.4 

4 

39 

Bromochloronitromethane 

benm 

4/10 

1950 

5/14 

97.4% 

1900 

54.0 

102.6 

5 

40 

Dibromonitromethane 

dbnm 

4/5 

3600 

5/14 

97.1% 

3500 

30.0 

105.0 

6 

41 

Benzyl chloride 

be 

4/5 

2300 

5/14 

99+% 

2300 

44.0 

101.2 

F 

1 

42 

30ppm AC Mix 

Bromopicrin 

tbnm 

4/5 

3300 

5/14 

99.0% 

3300 

9.1 

30.0 

2 

43 

Tribromoacetonitrile 

tban 

4/6 

3700 

5/14 

99.0% 

3700 

8.1 

30.0 

3 

44 

Bromodichloroacetonitrile 

bdean 

4/6 

2400 

5/10 

94.8% 

2300 

13.1 

30.1 

4 

45 

Dibromochloroacetonitrile 

dbcan 

4/10 

3500 

5/14 

42.1% 

1500 

20.0 

30.0 

5 

46 

Bromodichloronitromethane 

bdenm 

4/5 

3800 

5/14 

99.0% 

3800 

8.0 

30.4 

6 

47 

Dibromochloronitromethane 

dbcnm 

4/5 

4400 

5/14 

99.0% 

4400 

6.9 

30.4 


371 



















































































































Table 4. Improved extraction method comparison showing increased compound recoveries 

















tcm 

can 

cp 

TCAN 

DCAN 

BDCM 

tea 

denm 

BAN 

bdean 

bnm 

bean 


A Method 

107 

516 

137 

2093 

2022 

1489 

2690 

418 

7537 

4115 

2502 

2793 


B Method 

74 

272 

86 

1065 

1172 

310 

1674 

176 

2077 

1598 

506 

526 


% Improved 

45 

90 

59 

97 

73 

380 

61 

138 

263 

158 

394 

431 

















dcim 

bcnm 

111 tcp 

13dcp 

TBM 

dban 

dbcan 

1 ldbp 

dbnm 

11 ldcbp 

113tcp 

tbcm 

dbim 

A Method 

257 

3388 

2030 

1159 

291 

2547 

875 

3876 

2912 

577 

945 

102 

29 

B Method 

118 

2082 

632 

427 

173 

1441 

249 

2911 

1899 

169 

262 

49 

14 

% Improved 

118 

63 

221 

171 

68 

77 

251 

33 

53 

241 

261 

108 

107 
















TBA 

than 

BC 

CDIM 

1133tecp 

1113tecp 

tbnm 

BDIM 

111 tbp 

113tbp 

tim 

1133tebp 


A Method 

294 

1653 

12 

101 

184 

1868 

2 

265 

184 

1834 

247 

96 


B Method 

129 

621 

6 

47 

73 

431 

1 

107 

71 

1249 

76 

47 


% Improved 

128 

166 

100 

115 

152 

333 

100 

148 

159 

47 

225 

104 
















A Method 

Extract 30 mL sample with 3 mL MtBE + CuS04+ Na2S04 - 11 min shake 

B Method 

Extract 20 mL sample with 4ml MtBE + Na2S04 onlv - 5 min shake 


CONCLUSIONS 


The GC method produced various levels of data quality, as it was developed throughout 
the sampling period. The GC method became more reliable and robust over the development 
period. The final method was capable of measuring the 47 DBP analytes in this study. 


372 









































Table 5. Method reporting limit comparison of three analytical methods 





GC-LLE 

SPE 

P&T 

No. 

Compounds 

symbol 

mrl 

count 

mrl 

count 

mrl 

count 

A 

1 

lOOppm THM & 551B mix 

chloroform 

tem 

0.5 

1 



0.2 

1 

2 

bromodichloromethane 

bdem 

0.1 

2 

0.5 

1 

0.2 

2 

3 

chlorodibromomethane 

dbcm 

0.1 

3 

0.5 

2 

0.5 

3 

4 

bromoform 

tbm 

0.1 

4 

2.5 

3 

0.5 

4 

1 

Dichloroacetonitrile 

dean 

0.1 

5 

5 

4 

0.2 

5 

2 

bromochloroacetonitrile 

bean 

0.1 

6 

0.5 

5 

1.0 

6 

3 

dibromoacetonitrile 

dban 

0.1 

7 

.5 

6 



4 

trichloroacetonitrile 

tcan 

0.1 

8 

0.5 

7 



5 

1 , 1 -dichloroDropanone 

1,1-dcD 

0.1 

9 

1 

8 

0.5 

7 

6 

1,1.1 -trichloroDroDanone 

1,1.1 -tep 

0.1 

10 

1 

9 

0.5 

8 

7 

chloroDicrin 

tenm 

0.1 

n 

0.5 

10 

1.0 

9 

1 

1,1,2.2-tetrabromo-1 -chloroethane 

tebce 

0.5 

12 

2.5 

11 



B 

1 

lOOppm Halomethane mix 

Bromochloroiodomethane 

bcim 

5.0 

13 

1 

12 

0.5 

10 

2 

Dichloroiodomethane 

dcim 

0.5 

14 

1 

13 

0.5 

11 

3 

Dibromoiodomethane 

dbim 

0.5 

15 

1 

14 

0.5 

12 

4 

Chlorodiiodomethane 

edim 

0.1 

16 

2.5 

15 

0.5 

13 

5 

Bromodiiodomethane 

bdim 

0.5 

17 

5 

16 

0.5 

14 

6 

Iodoform 

tim 

2.0 

18 

2.5 

17 



7 

Tribromochloromethane 

tbcm 

0.5 

19 

0.5 

18 



C 

1 

lOOppm Halo(acetonitrile & acetaldt 

Bromoacetonitrile 

‘hyde) mix 

ban 

0.1 

20 

5 

19 

2.5 

15 

2 

Chloroacetonitrile 

can 

0.1 

21 



0.2 

16 

3 

Dichloroacetaldehvde 

dca 

0.5 

22 





4 

Bromochloroacetaldehyde 

bca 

0.5 

23 





5 

Tribromoacetaldehvde 

tba 

0.1 

24 

5 

20 



6 

chloral 

tea 

0.1 

25 





D 

1 

lOOppm Haloketone mix 

Chloropropanone 

cp 

0.1 

26 



0.5 

17 

2 

1,3-Dichloropropanone 

1,3-dcp 

0.1 

27 

2.5 

21 



3 

1.1,3-Trichloropropanone 

1.1.3-tcp 

0.1 

28 

2.5 

22 



4 

1.1,3.3-Tetrachloropropanone 

1.1.3.3-tecD 

0.1 

29 

5 

23 



5 

1,1,1,3-Tetrachloropropanone 

1,1,1.3-tecp 

0.1 

30 

5 

24 



6 

1 -Bromo 1 , 1 dichlorooropanone 

1-bl.ldcp 

0.1 

31 

1 

25 



7 

1.1-Dibromopropanone 

1,1 -dbp 

0.5 

32 

0.5 

26 

0.5 

18 

8 

1,1,1 -TribromoDropanone 

1.1.1-tbD 

0.1 

33 

5 

27 



9 

1.1,3-Tribromot>ropanone 

1.1.3-tbn 

0.1 

34 

5 

28 



10 

1,1,3,3-Tetrabromopropanone 

1,1,3,3-tebp 

0.5 

35 

5 

29 



E 

1 

lOOppm Halonitromethanes + be mi: 

Chloronitromethane 

: 

enm 


36 



0.5 

19 

2 

Bromonitromethane 

bnm 

0.1 

37 

2.5 

30 



3 

Dichloronitromethane 

denm 

0.1 

38 

0.25 

31 

0.5 

20 

4 

Bromochloronitromethane 

benm 

0.1 

39 

2.5 

32 



5 

Dibromonitromethane 

dbnm 

0.1 

40 

0.5 

33 



6 

Benzvl chloride 

be 

2.0 

41 

0.25 

34 

0.5 

21 

F 

1 

30ppm AC Mix 

Bromopicrin 

tbnm 

0.5 

42 





2 

Tribromoacetonitrile 

tban 

0.5 

43 





3 

Bromodichloroacetonitrile 

bdean 

0.5 

44 





4 

Dibromochloroacetonitrile 

dbcan 

0.5 

45 





5 

Bromodichloronitromethane 

bdenm 

0.5 

46 





6 

Dibromochloronitromethane 

dbcnm 

0.5 

47 






373 










































































































CLOSED-LOOP STRIPPING ANALYSIS METHOD 


Closed-loop stripping analysis (CLSA) has been successfully applied in the past for the 
determination of volatile organic compounds (VOCs) of intermediate molecular weight, 
including many taste-and-odor species. Typically, the compounds are stripped from 1 L of water 
by a recirculating stream of air, and trapped on a carbon filter cartridge. Extraction of the 
cartridge to a small, 20 pL volume produces unusually high concentration factors of 50,000:1 - 
enough to quantitate low ng/L levels. Although originally scheduled for the U.S. Environmental 
Protection Agency (USEPA) disinfection by-product (DBP) study, this technique proved less 
than desirable for continued research given the emerging successes of both solid phase extraction 
(SPE) and solid phase microextraction (SPME) techniques. It was discontinued during the 
Summer of 1999. 


EXPERIMENTAL 


Instrumentation 

The instrument used for this work was a VG TS-250 medium resolution mass 
spectrometer (VG Tritech, Manchester, England) equipped with a Digital PDP-11/53 computer 
(Digital Equipment Corporation, Maynard, MA). Samples were injected using a CTC A200S 
autosampler (Leap Technologies, Chapel Hill, NC). A HP 5890 (Hewlett-Packard, Palo Alto, 
CA) gas chromatograph was used for separations and partially controlled by an Optic 2 injector 
(AI Cambridge, Cambridge, England). 

Chromatography 

A DB-1 column was used (30-m, 0.25-mm ID, 1-pm film thickness) (J&W 
Scientific/Agilent, Folsom, CA). The GC oven temperature program used was based on EPA 
Method 551.1 (an initial temperature of 35 °C, which was held for 22 min, followed by an 
increase at a rate of 10 °C/min to 145 °C, which was held for 2 min; followed by an increase at a 
rate of 20 °C/min to 225 °C, which was held for 15 min). 

General Procedure 

The procedure for CLSA was taken from Standard Methods for the Examination of 
Water and Wastewater (20 th ed., 1998). For standards, 900 mL of organic pure water (OPW) 
was placed into a 1-L glass stripping bottle. Seventy-two grams of sodium sulfate were added 
with rapid mixing until the salt was mostly dissolved. The sample was then spiked with a 
cocktail mix, covered, placed into a water bath at room temperature (22 °C), and stripped for 2 
hours. The 1.5 mg carbon filter was extracted with dichloromethane, carbon disulfide (CS 2 ), or 
methyl tertiary butyl ether (MtBE) and brought to a final volume of 20 pL, if needed. The 
infinitesimally small sample was transferred into a special conical-shaped autosampler vial for 
storage. After a 2 pL injection to the GC, the remaining extract was covered with a fresh Teflon 
cap and stored in the freezer for future reference. A detailed description of the method can be 
also found at Krasner et al. (1983). 


374 


RESULTS AND DISCUSSION 


Initial DBP Testing - Extraction Efficiency 

Stripping efficiencies can be optimized by adjusting stripping time, temperature, and use 
of salt to increase the ionic strength of the water. A preliminary check of DBP compatibility was 
done using a mixture of DBPs spiked in organic pure water. The spiking mix (5 pL of the 200 
ppm mixture) was added to 900 mL of pure water to give an actual concentration of 1.1 pg/L in 
the water. At 100% analyte recovery, this is equivalent to a 50-ppm unextracted standard. 
Stripping time was two hours. 

Table 1. Extraction efficiency of select DBPs 


Compound 

RT (min) 

No Salt 
CS 2 

No Salt 
CS 2 DUP 

72 g Salt 
CS 2 

72 g Salt 
CS 2 DUP 

72 g Salt 
MeCI 2 

72 g Salt 
MeCI 2 DUP 

chloroacetonitrile 

7.3 

ND 

ND 

ND 

ND 

ND 

ND 

chloropropanone 

7.9 

ND 

ND 

ND 

ND 

ND 

ND 

carbon tetrachloride 

8.7 

6% 

ND 

ND 

9% 

3% 

15% 

bromoacetonitrile 

15.2 

ND 

ND 

ND 

ND 

ND 

ND 

dichloroiodomethane 

24.8 

14% 

15% 

24% 

19% 

25% 

44% 

1,3-dichloropropanone 

27.5 

ND 

ND 

ND 

ND 

ND 

ND 

bromochloroiodomethane 

29.6 

37% 

23% 

50% 

36% 

44% 

71% 

1,1,3-trichloropropanone 

31.0 

ND 

ND 

ND 

ND 

ND 

ND 

chlorodiiodomethane 

33.2 

37% 

22% 

49% 

40% 

57% 

76% 

bromodiiodomethane 

35.7 

26% 

19% 

60% 

40% 

47% 

61% 

hexachloropropanone 

37.4 

ND 

ND 

ND 

ND 

ND 

ND 

iodoform 

38.1 

8% 6% 

22% 

14% 

21% 

24% 


This preliminary check of the CLSA method pointed out potential problems that would 
need to be addressed. First, the results were highly irreproducible for duplicate analyses without 
any internal standard. The sample concentrations listed in Table 1 were obtained from raw area 
counts of the compound peaks. There can be many variables introduced during the stripping 
procedure to cause such a wide variance in results, such as minute air leaks in the stripping 
apparatus, differences in the filter flow rates (age of filter, contamination), temperature 
differences during stripping, and analyte loss during the final extraction. For some haloketones 
and haloacetonitriles (chloropropanone, 1,3-dichloropropanone, 1,1,3-trichloropropanone, 
chloroacetonitrile, and bromoacetonitrile), there were no detectable recoveries. For the iodinated 
THMs and carbon tetrachloride, results showed that the use of salt improved the stripping 
efficiency. Also, dichloromethane was a better solvent compared to carbon disulfide. 


375 





















































CHClBrI 



Figure 1. Two-hour closed-loop stripping analysis of iodinated THMs and carbon 
tetrachloride. Elution solvent was dichloromethane. 

Figure 1 shows the best case scenario for iodo-THMs and carbon tetrachloride, utilizing 
72 grams of sodium sulfate and dichloromethane for extraction. Stripping time was 2 hours. 

Traditional DBPs 

Initial attempts to apply closed-loop stripping analysis to the new DBPs that are part of 
this project failed to yield immediate results for any compounds other than iodinated species and 
carbon tetrachloride. The targeted compounds included chloropropanone, 1,3- 
dichloropropanone, 1,1,3-trichloropropanone, hexachloropropanone (later found to immediately 
hydrolyze in water), bromoacetonitrile, and chloroacetonitrile. 


376 























100 


DCAN 



TCAN 


DBAN 


1,1-DCP 


6 000 10.000 12 000 14 000 


1,1,1-TCP 


BCAN 





Figure 2. a) Direct injection of 200 ppm of DBP mixture for comparison, b) CLSA extract 
of DBP mixture in MtBE. 

It was suggested that some of the EPA method 551.1 DBPs should be attempted since 
there was some evidence that it should be possible to strip these compounds (Croue and 
Reckhow 1989). Therefore, the following standards were obtained and analysed by CLSA: 
dichloro-, dibromo-, and trichloroacetonitrile, and 1,1-dichloro-, and 1,1,1-trichloropropanone. 
Results from these compounds were more promising. A series of experiments was performed to 
evaluate the effect of extraction solvent and stripping time for the compounds. All of the 
compounds were spiked both with the DBP mixture and an added 1-chlorooctane internal 
standard/surrogate. For consistency and ease of results interpretation, all samples were stripped 
on the same apparatus and on the same day. Three solvents were tested, including MtBE, 
dichloromethane, and carbon disulfide. A 30-min stripping time was also evaluated as an 
alternative to the traditional 1-2 hour time. 

The MtBE solvent peak eluted at 4 min and continued until about 5.5 min, with tailing. 
Quantitative peaks occurred after 7 min and continued throughout the 50-min run. The 
1-chlorooctane internal standard eluted at 34 min and was not shown in Figure 2. All peaks were 
identified using their NIST library mass spectra. 

Overall, MtBE was best at removing the compounds from the carbon filter, followed by 
MeCh, and then CS 2 . An additional benefit of using MtBE is that it allows extracts to be run on 
a GC equipped with an electron capture detector (ECD), which is not possible for chlorinated 
solvents. In addition, it was confirmed that a 1-hour strip was preferred over a 30-min strip time, 


377 

































although there is a point of diminishing returns. Generally, anything over two hours does not 
increase analyte recoveries significantly. 

The use of higher stripping temperatures improved stripping efficiency. However, 
attempts at 40 °C were unsuccessful because of moisture condensation onto the carbon filter. 
Despite attempts to heat the entire air system using heater tape to avoid cold spots, the large 
volume of humid air moving through the system inevitably spoiled any attempts to produce 
successful results. Commercially-designed systems (e.g. Mass Evolution, Inc., Houston, TX) 
can use slightly wider glass cartridge holders and heating blocks to allow higher temperature 
operation. 


CONCLUSIONS 

At the start of this work, many of the DBPs that were planned for the Nationwide DBP 
Occurrence Study had yet to be received. This work represents only a portion of the compounds 
that could have been tested. But, based on these preliminary results, it seems unlikely that CLSA 
would have been a good universal screening device for new DBPs (i.e. limited compatibility, 
large sampling requirement, poor reproducibility). Table 2 lists the compounds tested and 
whether they were amenable to closed-loop stripping analysis. 


REFERENCES 

Croue, J.-P., and D. A. Reckhow. Destruction of chlorination byproducts with sulfite. 
Environmental Science & Technology 23(11): 1412 (1989). 

Krasner, S. W., C. J. Hwang, and M. J. McGuire. Water Science & Technology 15: 127 (1983). 

Munch, D. J., and D. P. Hautman. Method 551.1. Determination of 
ChlorinationDisinfection Byproducts, Chlorinated Solvents, and Halogenated 
Pesticides/Herbicides in Drinking Water by Liquid-Liquid Extraction and Gas Chromatography 
with Electron Capture Detection. Methods for the Determination of Organic Compounds in 
Drinking Water, Supplement III, EPA-600/R-95/131. Cincinnati, OH: U.S. Environmental 
Protection Agency, 1995. 

Standard Methods for the Examination of Water and Wastewater, 20 th ed.\ American Public 
Health Association: Washington, D.C., 1998. 


378 


Table 2. Summary of compounds tested for closed-loop stripping analysis 


Compound 

CLSA Extraction? 

Iodomethanes 


D ichloro iodomethane 

YES 

Bromochloriodomethane 

YES 

Dibromoiodomethane 

YES 

Chlorodiiodomethane 

YES 

Bromodiiodomethane 

YES 

Triiodomethane (iodoform) 

YES 

Haloacetonitriles 


Chloroacetonitrile 

NO 

Bromoacetonitrile 

NO 

Dichloroacetonitrile 

YES 

Bromochloroacetonitrile 

YES 

Dibromoacetonitrile 

YES 

Trichloroacetonitrile 

YES 

Haloketones 


Chloropropanone 

NO 

1,1 -Dichloropropanone 

NO 

1,3-Dichloropropanone 

NO 

1,1,1 -Trichloropropanone 

YES 

1,1,3-Trichloropropanone 

NO 

Misc. Compounds 


Carbon tetrachloride 

YES 


379 


























PURGE-AND-TRAP GAS CHROMATOGRAPHY/MASS SPECTROMETRY METHOD 


The method used for the analysis of volatile organic compounds (VOCs) and volatile and 
semi-volatile disinfection by-products was a purge-and-trap (P&T) gas chromatography (GC)/ 
mass spectrometry (MS) method based on U. S. Environmental Protection Agency (USEPA) 
Method 524.2 (Figure 1). The methods development included the addition of several volatile 
and semi-volatile DBPs and some changes to the GC conditions (i.e., analytical column and 
column temperature program). 


EXPERIMENTAL 


Instrumentation 

The instrument used was a Varian Saturn 2000 mass spectrometer (Varian Analytical 
Associates Inc., Walnut Creek, CA) equipped with a 3800 gas chromatograph (GC). A Tekmar 
LSC2000 concentrator (Tekmar Co., Cincinnati, OH) and a Varian Archon P&T autosampler 
(Varian) were used for automated sampling. 

Sample Preparation 

Information about the analytical standards used for this P&T method are outlined in 
Table 1. Standard mixes were obtained from Ultra Scientific (North Kingstown, RI), which 
contained the following compounds at a level of 5000 pg/mL each in acetone: dichloro-, 
bromochloro-, dibromo-, and trichloroacetonitrile, 1,1 -dichloro- and 1,1,1 -trichloropropanone, 
and chloropicrin. The trihalomethane mix (Ultra Scientific) contained chloroform, 
bromodichloromethane, dibromochloromethane, and bromoform at a level of 5000 pg/mL each 
in methanol. Each of the VOCs was prepared from separate, individual solutions containing 
chloromethane, bromomethane, dibromomethane, bromochloromethane, carbon tetrachloride, 
methyl tertiary butyl ether, and methyl ethyl ketone, all of which were obtained from Supelco 
(Bellefonte, PA) at either a 2000 or 5000 pg/mL level. An EPA Method 524.2 Fortification 
Solution (Supelco) contained the internal standards for this analysis, fluorobenzene (FB), and the 
surrogates, 4-bromofluorobenzene (BFB) and l,2-dichlorobenzene-d4(l,2-DCP-d4), at 
concentrations of 2000 pg/mL each in methanol. The other target DBPs were obtained in the 
highest purity available from sources listed in Table 1. 

Stock Solutions from Neat Compounds 

For all of these new, target DBPs that were being investigated in this project, stock 
solutions were prepared by either of two different methods. First, those DBPs that were prepared 
from pure, neat compound as follows. An accurately measured portion of 1.0 mL of methanol 
solvent (Burdick & Jackson, purge and trap grade, Muskegon, MI) was placed into a capped 2.0 
mL autosampler vial and weighed. Approximately 2-3 pL of the neat compound was pulled into 
a cleaned syringe and spiked into the solvent after piercing the septum. The additional weight by 
difference, between 2-5 mg, was used to calculate the concentration of each compound. The 
septum caps were changed before storage. Alternatively, those DBPs that were solid were 
prepared by weighing the standard in the autosampler vial and adding solvent. 


380 


25-mL sample aliquot 



1-pL 

“fortification solution” 


Sparge with helium for 
11 minutes onto 
VOCARB 4000 trap 



Desorb trap at 240 °C for 4 minutes 


V 


Transfer to GC injector 


V 


Analysis by GC/MS 


Figure 1. Summary of the Purge and Trap-GC/MS method used for analyzing DBPs in 
drinking water. 


381 


















Standard Spiking Solutions 

A standard DBP spiking solution was prepared by diluting all of the target compounds to 
a final volume of 1 mL of methanol (Burdick & Jackson). Table 2 outlines the concentrations 
and volumes of the standard solutions used to prepare the DBP spiking solution. This solution 
was used to prepare P&T calibration standards. 

Internal Standard and Surrogates 

The internal standard and surrogates were prepared as follows. Into a 5-mL volumetric 
flask was measured 4.5 mL of methanol. A 62.5 pL aliquot of the “fortification solution” was 
added to the methanol and the volume brought up to 5 mL. This solution was then transferred to 
the Archon autosampler standard solution reservoir. The Archon autosampler then adds a 1 pL 
standard addition to the sample water prior to purge-and-trap concentration for a final 
concentration of 1 pg/L. 

Calibration Standards and Check Samples 

Calibration standards were prepared at the levels of 0.2, 0.5, 1.0, 2.5, 5.0, 10, 20, and 40 
pg/L. An appropriate amount of the DBP spiking solution was added to a 50-mL volumetric 
flask containing purified water (Ultra Resi-analyzed, J.T. Baker, Phillipsburg, NJ). This solution 
was then transferred to a 40-mL vial containing 2 drops of 1 M H 2 SO 4 to bring the pH down to 
3-3.5, then capped with an open-top cap and Teflon-silicon septa. Calibration standards were 
prepared every time a set of samples was analyzed, approximately every two weeks. 

Check standards were analyzed at the beginning and end of each analytical run. These 
check standards were prepared in the same way as calibration standards, but at the 5 or 10 pg/L 
level. 


382 


Table 1. P&T-GC/MS DBP target analyte sources 


Compound Class/DBP 

Source 

Compound Class/DBP 

Source 

THM Mix 

Ultra Scientific 3 

Halonitromethanes 


Chloroform 


Chloronitromethane 

Can Syn e ; Helix 

Bromodichloromethane 


Bromonitromethane 

Aldrich 

Dibromochloromethane 


Dichloronitromethane 

Can Syn; Helix 

Bromoform 


Haloacetonitriles 


551B Mix 

Ultra Scientific 

Chloroacetonitrile 

Aldrich 

Dichloroacetonitrile 


Bromoacetonitrile 

Aldrich 

Bromochloroacetonitrile 

Dibromoacetonitrile 


VOCs 


1,1 -Dichloropropanone 


Chloromethane 

Supelco g 

1,1,1 -Trichloropropanone 


Bromomethane 

Supelco 

Chloropicrin 


Dibromomethane 

Supelco 



Bromochloromethane 

Supelco 

Iodomethanes 


Carbon tetrachloride 

Supelco 

Dichloroiodomethane 

AGBAR b 

MTBE 

Supelco 

Bromochloroiodomethane 

AGBAR 

MEK 

Supelco 

Dibromoiodomethane 

AGBAR 



Chlorodiiodomethane 

AGBAR 

Miscellaneous 


Bromodiiodomethane 

AGBAR 

Benzyl chloride 

Fluka 

Haloketones 


Internal Standard 


Chloropropanone 

Aldrich f 

Fluorobenzene 

Supelco 

1,3-Dichloropropanone 

Aldrich 



1 ,1,3-Trichloropropanone 

Fluka h 

Surrogates 


1,1 -Dibromopropanone 

UNC c ; Helix d 

4-Bromofluorobenzene 

Supelco 




Supelco 



1,2-Dichlorobenzene-d4 



a Ultra Scientific (North Kingstown, R.I.) 
b AGBAR: Aigues of Barcelona (Spain) 

c UNC: Synthesized by University of North Carolina at Chapel Hill 
d Helix Biotech (New Westminster, B.C., Canada) 
e Can Syn: Synthesized by Can Syn Chem Corp. (Toronto, ON, Canada) 
f Aldrich (St. Louis, Mo.) 

8 Supelco (Bellefonte, Pa.) 
h Fluka (St. Louis, Mo.) 


383 
















Table 2. Standard spiking solution preparation 


Compound 

Abbrev. 

Name 

Cone. 

(mg/L) 

Purity 

Adjusted 

Cone. 

(mg/L) 

Actual 

Transfer Vol. (uL) 
50 mg/L Std 

Final 

Concentration 
(50 mg/L Std) 

THM/551B Mix 







Chloroform 

TCM 

5000 

99+% 

5000 

10 

50 

Bromodichloromethane 

BDCM 

5000 

99+% 

5000 

10 

50 

Dibromochloromethane 

DBCM 

5000 

99+% 

5000 

10 

50 

Bromoform 

TBM 

5000 

99+% 

5000 

10 

50 

EPA 55IB Mix 







Dichloroacetonitrile 

DC AN 

5000 

99+% 

5000 

10 

50 

Bromochloroacetonitrile 

BCAN 

5000 

99+% 

5000 

10 

50 

Dibromoacetonitrile 

DBAN 

5000 

99+% 

5000 

10 

50 

1,1 -Dichloropropanone 

1,1 -DCP 

5000 

99+% 

5000 

10 

50 

1,1,1 -Trichloropropanone 

1,1,1-TCP 

5000 

99+% 

5000 

10 

50 

Chloropicrin 

TCNM 

5000 

99+% 

5000 

10 

50 

Iodomethane Mix 







Dichloroiodomethane 

DCIM 

3500 

93.3% 

3250 

17 

55.25 

Bromochloroiodomethane 

BCIM 

5200 

96.7% 

5050 

9.9 

49.995 

Dibromoiodomethane 

DBIM 

3400 

97.2% 

3300 

15 

49.5 

Chlorodiiodomethane 

CDIM 

4200 

86.3% 

3600 

14 

50.4 

Bromodiiodomethane 

BDIM 

4800 

91.5% 

4400 

11 

48.4 

Haloacetonitrile Mix 







Chloroacetonitrile 

CAN 

3700 

99+% 

3700 

13.5 

49.95 

Bromoacetonitrile 

BAN 

5700 

99+% 

5700 

9 

51.3 

Haloketone Mix 







Chloropropanone 

CP 

2700 

98.1% 

2650 

19 

50.35 

1,3-Dichloropropanone 

1,3-DCP 

4100 

99+% 

4100 

12 

49.2 

1,1,3-Trichloropropanone 

1,1,3-TCP 

3500 

97.7% 

3400 

15 

51 

1,1 -Dibromopropanone 

1,1-DBP 

3300 

94.1% 

3100 

16 

49.6 

Halonitromethane Mix 







Chloronitromethane 

CNM 

2700 

98.8% 

2650 

19 

50.35 

Bromonitromethane 

BNM 

5200 

99+% 

5200 

10 

52 

Dichloronitromethane 

DCNM 

5000 

99+% 

5000 

10 

50 

Miscellaneous 







Benzyl chloride 

BC 

3100 

99+% 

3100 

16 

49.6 

Volatiles Mix 







Chloromethane 

CIMe 

2000 

99+% 

2000 

25 

50 

Bromomethane 

BrMe 

2000 

99+% 

2000 

25 

50 

Dibromomethane 

DBM 

2000 

99+% 

2000 

25 

50 

Bromochloromethane 

BCM 

2000 

99+% 

2000 

25 

50 

Carbon Tetrachloride 

CC14 

5000 

99+% 

5000 

10 

50 

MtBE 


2000 

99+% 

2000 

25 

50 

MEK 


2000 

99+% 

2000 

25 

50 


384 



















Gas Chromatography 

A DB-624 GC column was used (30-m, 0.25-mm ID, 1.4-pm film thickness) (J & W 
Scientific/Agilent, Folsom, CA). The 1079 injector was set at 220 °C with a split ratio of 30:1. 
The column temperature program used was developed for a wide range of VOCs: an initial oven 
temperature of 35 °C, which was held for 4 minutes, followed by an increase at a rate of 4 
°C/min to 50 °C, with no time hold, followed by an increase at a rate of 10 °C/min to 175 °C, 
which was held for 2 min, then a final increase at a rate of 20 °C/min to 200 °C, which was held 
for 1.5 min. The total temperature run time was 25 min. This temperature program was used 
until January 2002. 

For analyses performed after June 2001, a DB-1 GC column was used (30-m, 0.25-mm 
ID, 1-pm film thickness) (J & W Scientific/Agilent), and the 1079 injector was set at 220 °C 
with a split ratio of 20:1. The same column temperature program that was used with the DB-624 
column was used with the DB-1 column. A modified temperature program was used beginning 
in January 2002 to match the work that was developed for the LLE-GC/ECD method: 
isothermal column temperature at 35 °C held for 23 min, followed by an increase at a rate of 4 
°C/min to 139 °C, with no time hold, followed by an increase at a rate of 27.7 °C/min to a final 
temperature of 250 °C, which was held for 5 min. Total run time was 58.0 min. 

Mass Spectrometry 

Electron ionization (El) was used on the Saturn GC/mass spectrometer. Table 3 outlines 
the mass spectrometer parameters used for this method. 

Purge-and-Trap (P&T) Analysis 

The P&T concentration was carried out using the Varian Archon autosampler, which 
prepared a 25 mL aliquot of sample for transfer to the Tekmar LSC 2000 concentrator. The 40- 
mL sample vials were placed in the Archon autosampler, where a 25-mL aliquot was taken. 

Prior to transfer to the LSC 2000, 1 pL of the “fortification solution” was added. Once the 
sample was transferred to the LSC 2000 concentrator, it was sparged for 11 min at room 
temperature with helium, at a flow rate of 15 mL/min, onto a VOCARB 4000 trap (Supelco). 

The analysis continued with a desorption preheating of the trap to 240 °C and final desorption of 
the sample for 4 min. At this point the sample was then “injected” onto the Varian GC attached 
to the Saturn mass spectrometer. 

Sample Preservation 

Samples were collected in nominal 40-mL vials with Teflon-faced silicon septa and 
polypropylene open-top screw caps. The sample vials were filled with 1.4 mg of ascorbic acid to 
quench any residual oxidant present at the time of sampling. A solution of freshly prepared 
sulfuric acid was used to reduce the pH to within the 3-3.5 range to provide stability of the target 
analytes and was added prior to capping the sample bottle. This reduction in pH was necessary 
in order to eliminate the possibility of base-catalyzed hydrolysis that many of the target analytes 
are susceptible to at higher pH. Samples were stored during transit to the laboratory in ice chests 
with ice-packs to keep them cold. Upon arrival at the laboratory, the samples were placed in a 
10 °C refrigerator for longer-term storage. 


385 


Table 3. Saturn ion trap mass spectrometer conditions 


Segment 1 filament off, no data acquisition 




Segment 2 start time 

1.0 min. 



end time 

50 min. 



emission current 

25 pA 



scan time 

1.00 sec 



low mass 

41 m/z 



high mass 

400 m/z 



ionization mode 

El AGC 1 



ion preparation technique 

none 



El auto mode: 





Mass range 

ion. storage 

ion. time 



level 

factor 

scan segment 1 

10 to 70 

35 m/z 

120% 

scan segment 2 

71 to 78 

35 m/z 

70% 

scan segment 3 

79 to 150 

35 m/z 

100% 

scan segment 4 

151 to 650 

35 m/z 

68% 

maximum ionization time 

25000 psec 



target TIC 

30000 




counts 



prescan ionization time 

100 psec 



background mass 

45 m/z 



RF dump value 

650 m/z 




1 AGC - automatic gain control 


RESULTS AND DISCUSSION 


Detection Limits 

Detection limits were determined in two different ways. The first was strictly by 
observing the lowest level standard that could be seen and measuring the peak area counts. 
Based on a signal-to-noise ratio of 5 or greater, a detection limit was initially used. This 
technique resulted in a wide variety of observed levels for each of the target analytes. The 
second method used was a statistical evaluation of seven replicates run on two successive days. 
This method yielded significantly higher detection limits for the target analytes. The method 
detection limit (MDL) was determined for each analyte as follows: 


386 





MDL = t (S) 

t = 2.65 (student t value for 13 degrees of freedom and 99 percent 
confidence level) 

S = standard deviation of the 14 replicate analyses 

These MDLs were used as minimum reporting levels (MRLs), except where the instrumental 
detection limit proved to be higher. Often, the MRLs corresponded to the lowest level standard 
on the calibration curve. Table 4 shows the DL and MDL for each of the P&T target 
compounds. Where NA is reported for a compound, the opportunity to calculate the MDL was 
not available, as the compound was added very late in the project for P&T analysis. This table 
shows that these compounds are amenable to P&T analysis. 


Table 4. Detection limits for purge-and-trap DBP analysis 


Compound 

DL 

(Pg/L) 

MDL 

(Pg/L) 

Compound 

DL 

(Pg/L) 

MDL 

(Pg/L) 

Chloroform 

0.2 

0.684 

Chloromethane 

0.2 

0.903 

Bromodichloromethane 

0.2 

0.732 

Bromomethane 

0.2 

1.02 

Dibromochloromethane 

0.2 

0.727 

Dibromomethane 

0.5 

0.775 

Bromoform 

0.5 

0.716 

Bromochloromethane 

0.5 

0.654 




Carbon Tetrachloride 

0.2 

0.906 

Dichloroacetonitrile 

0.2 

0.945 

MtBE 

0.2 

0.721 

Bromochloroacetonitrile 

0.5 

NA 

Methyl ethyl ketone 

0.5 

0.617 

Dibromoacetonitrile 

0.5 

NA 




1,1 -Dichloropropanone 

0.5 

0.775 

Chloropropanone 

0.5 

1.19 

1,1,1 -Trichloropropanone 

0.5 

0.755 

1,3-Dichloropropanone 

0.5 

NA 

Chloropicrin 

0.5 

NA 

1,1,3-Trichloropropanone 

0.5 

NA 




1,1 -Dibromopropanone 

0.5 

NA 

Dichloroiodomethane 

0.5 

0.819 




Bromochloroiodomethane 

0.5 

0.748 

Chloronitromethane 

0.5 

NA 

Dibromoiodomethane 

0.5 

1.28 

Bromonitromethane 

0.5 

NA 

Chlorodiiodomethane 

0.5 

0.669 

Dichloronitromethane 

0.5 

NA 

Bromodiiodomethane 

0.5 

0.811 







Chloroacetonitrile 

0.2 

0.775 

Benzyl chloride 

0.5 

0.624 

Bromoacetonitrile 

2.5 

1.12 


DL = detection limit; MDL = method detection limit 


387 






Evaluation of Analytical Columns 

A DB-624 column was initially installed on the Saturn GC/MS in the early phase of the 
project. This was due to the fact that the instrument was shared with another group analyzing 
VOCs for compliance purposes. As the project progressed, it was determined that other 
arrangements needed to be made in order to accommodate the addition of analyzing solid phase 
extraction (SPE) samples on the same instrument. 

The DB-624 column is a medium polarity column and is the column used by the 
Metropolitan Water District of Southern California (MWDSC) for EPA Method 524.2 (P&T) for 
compliance VOC monitoring. An evaluation of this column compared to the DB-1 was 
necessary in order to determine whether it was suitable for the SPE method. It was determined, 
and discussed in further detail in the SPE section, that the DB-624 column was unsuitable for the 
SPE method. 

A total ion chromatogram (TIC) comparison between the DB-624 column and a DB-1 
column is shown in Figure 2. Because the DB-1 column showed significantly improved 
resolution of the analytes, it was determined that this column would be optimal for P&T 
analyses. One of the problems associated with the use of the DB-624 column was the coelution 
of some target compounds, such as chloropropanone and bromodichloromethane. This was not a 
problem with the DB-1 column. 

Other Changes to P&T Method 

Other changes to the P&T method included the use of only a selected list of VOCs 
combined with the other target DBPs. Initially the P&T method relied on the use of two separate 
sets of calibration standards and separate calibration curves. By paring down the VOC list to 
only the target VOCs of interest in this study and combining them with the target DBPs had 
some major advantages. One advantage was a simpler calibration step in which all of the P&T 
method compounds could be analyzed in a single P&T run. This eliminated the need to process 
sample data files twice. Also, the elimination of any coelution interferences between those 
VOCs that were part of a larger cocktail of analytes and some of the target DBPs. Some of the 
target DBPs that exhibited coelution problems were chloropropanone, bromodichloromethane, 
1,1,1-trichloropropanone, chlorodiiodomethane, and bromochloroiodomethane. These 
compounds were difficult to separate from VOCs that were contained in the original cocktail of 
more than 60 VOC compounds. Chloropropanone and bromodichloromethane were resolved 
simply by changing to the DB-1 column. 

Improved Temperature Program 

An updated GC column temperature program was used beginning in January 2002. 

Figure 3 shows a TIC for a 10 pg/L standard analyzed with the updated column temperature 
program. This improvement allowed for better separation of the analyte peaks. The temperature 
program used was similar to the one used for the LLE and SPE analyses, except that a lower 
final temperature of 250 °C was used instead of 301 °C. 


388 



Figure 2. Comparison TIC between DB-624 and DB-1 columns for purge-and-trap analysis. 

A) All target DBPs on DB-1 column; B) VOCs on DB-624 column; C) Target DBPs on DB-624 
column. 


389 










































































































Figure 3. TIC for a 10 pg/L Purge-and-trap DBP/VOC standard on DB-1 column with extended column temperature 
program. 


390 






























Holding Study 

Sample stability data was used from previous work done using SPE or LLE 
methods, and was not repeated for the P&T analysis. The P&T analysis used the same 
sample bottles and preservation scheme as the SPE and LLE methods (ascorbic acid 
preserved) samples. To summarize these results by compound family: 


VOCs- 
THMs - 
Iodo-THMs - 
Haloacetonitriles - 
Chloropropanones - 
Halonitromethanes - 
Miscellaneous - 


Stable through Day 21. 

Stable through Day 21. 

Stable through Day 21. 

Stable through Day 21 
Stable through Day 21. 

Stable through Day 21. 

Benzyl chloride showed a slow decay. 


Samples were generally analyzed within 2-3 days after receipt at MWDSC. This allowed 
for time to reanalyze samples if necessary and to allow for the instrument to be used for 
the SPE analyses later. 


Improvements on the Saturn Ion-trap 

One of the improvements made for the analysis of the P&T analytes was the use 
of multiple quantitation ions to increase the sensitivity. In previous analyses, a single ion 
was used to quantitate analyte peaks. The result of this change was an increase in 
selectivity for the target analytes. 


CONCLUSIONS 

EPA Method 524.2 was used as the basis for these analytes, but it was modified in 
such a way that an expanded list of compounds could be analyzed. The only real changes 
were the analytical column used and the column temperature program. The P&T 
concentrator parameters and the internal standard/surrogates remained the same. This 
P&T method was capable of analyzing for 32 DBPs as part of the Nationwide DBP 
Occurrence Study. Of those 32 compounds included in this method, 11 were originally 
analyzed as VOC compounds. The remaining 21 compounds represent additional 
compounds not normally associated with a P&T type of analysis. This P&T method 
allowed for confirmation of results obtained from SPE and LLE methods, as well as the 
solid phase microextraction method developed later. 


391 


REFERENCES 


Munch, D. J., and D. P. Hautman. Method 551.1. Determination of 
ChlorinationDisinfection Byproducts, Chlorinated Solvents, and Halogenated 
Pesticides/Herbicides in Drinking Water by Liquid-Liquid Extraction and Gas 
Chromatography with Electron Capture Detection. Methods for the Determination of 
Organic Compounds in Drinking Water, Supplement III, EPA-600/R-95/131. Cincinnati, 
OH: U.S. Environmental Protection Agency, 1995. 


392 


METHOD FOR HALOGENATED FURANONES (MX-ANALOGUES) 

METHOD SUMMARY 


For the Nationwide DBP Occurrence Study, a method was developed for the 
analysis of the following halogenated furanones: MX, MCA, BMX-1, BMX-2, and their 
open forms (see full names in Glossary; structures in Figure 1). This method evolved from 
the previous methods of Holmbom et al. (1981), Hemming et al. (1986), and Kronberg et al. 
(1988, 1991) which required large volumes of water for concentration onto XAD resins and 
lengthy processing times that endanger the stability of the MX-analogues. Because of their 
complexity, these methods do not incorporate adequate quality assurance (QA)/quality 
control (QC) components to validate their resulting data. In order to accurately assess the 
concentrations of MX-analogues in drinking water, a liquid-liquid extraction (LLE)-gas 
chromatography (GC)-electron capture detection (ECD) method was developed, which uses 
smaller sample volumes and shorter processing times to protect compound stability. 

For the new method, the chlorine quenching agent, ammonium sulfate [100 pL of 40 
mg/mL (NH 4 ) 2 S 04 ] was added to acid-washed amber glass sample bottles (250 mL) fitted 
with Teflon-lined screw caps prior to sending the bottles to the water treatment plants for 
duplicate sample collection. Field blanks filled with DIW were included. Sample bottles 
were returned to UNC in a cooler with ice packs, shipped by overnight delivery. 
Immediately upon arrival, or within 5 hours, the samples were removed from the cooler, and 
analyzed for MX and MCA after they had reached room temperature (the BMX analysis 
was performed one week following receipt of samples). The calibration samples were 
prepared on the day of extraction, at 0, 50, and 250 ng/L MX and MCA (or 0, 100, and 500 
ng/L BMX-1,2,3) in DIW in 250 mL volumetric flasks. One sample from each plant was 
collected in a 1 L amber bottle to allow for a matrix spike sample (250 ng/L MX and MCA 
or 500 ng/L BMX-1,2,3). 

Prior to extraction, each 250-mL sample was spiked with MBA as a surrogate 
standard at 250 ng/L, and acidified to pH 2 with sulfuric acid. Each sample was extracted 
twice with 50 mL of MtBE in a 500 mL glass separatory funnel. The combined extract was 
collected in a 125 mL amber bottle (fitted with a Teflon-lined screw cap) containing two 
approximately 8 g of calcium chloride (CaCC), and shaken to remove residual water 
dissolved in the MtBE. The extract was transferred (without CaCh) to a 250 mL round 
bottomed flask and reduced to a few mLs by rotary evaporation at 40°C. The reduced 
extract was transferred to a 20 mL centrifuge tube, with a few mL rinse of MtBE. This 
extract was further reduced to about 500 pL by nitrogen (N 2 ) gas. To this reduced MtBE 
extract was added 2 mL of 14% BF 3 /MeOH, and the tube was sealed with a Teflon-lined 
screw cap. The solution was mixed and heated at 70°C for 4 hours in an oven. After 
returning to room temperature, the derivatization agent and pH were neutralized by adding 4 
mL of 10% NaHC 03 , with mixing. 


i 


393 



Cl 



Cl 




OH Cl 
ox-EMX 



MCA (mucochloric acid) 


open form MCA 


Cl Br 




Br 



O 


Figure 1. Structures of halogenated furanones (MX-analogues). 


394 





























The MXR-analogues were back-extracted twice into 1 mL hexane. The combined 2 
mL hexane extract was collected in a 10 mL centrifuge tube and reduced to <250 |uL by N 2 
gas. The internal standard hexachlorobenzene (HCB) was added (5 pL of 500 ng/mL 
HCB/hexane) to the hexane extract, which was brought to a final volume of 250 pL. The 
final hexane extract was transferred to an amber crimp-topped vial with a 300 pL glass 
insert for GC-ECD analysis. The MX and MCA samples were separated by gas 
chromatography on a HP-5MS column (30-m x 0.25 mm ID x 0.25 pm film thickness) at a 
temperature program of 105°C for 1 min, 2.5°C/min to 140°C, and 20°C/min to 280°C, with 
an injection temperature of 200°C and a detector temperature of 300°C. The BMX samples 
were separated by gas chromatography on a Phenomenex ZB5 column (60-m x 0.25 mm ID 
x 0.25 pm film thickness) at a temperature program of 100°C for 1 min, 20°C/min to 150°C, 
l°C/min to 185°C, and 20°C/min to 280°C, with an injection temperature of 160°C and a 
detector temperature of 300°C. Calibration curves for each component were constructed 
using analyte area relative to the internal standard (HCB). Calculated concentrations of 
analytes were corrected by percent recovery in the matrix spike sample. Relative areas of 
the analytes to the surrogate standard (MBA) were not reliable for duplicate calibration 
samples. 

Because method development continued during the first year of plant surveys, no 
halogenated furanone data is presented during the first two seasons. The plant data and 
discussion is included among the results for each utility elsewhere in this report. The 
minimum reportable limit for MX-analogues was 40 ng/L. Non-zero concentrations below 
40 ng/L are given in parentheses, to indicate relative values extrapolated from the 
calibration curves. 


INTRODUCTION 

The detection of the disinfection by-product (DBP) 3-chloro-4-(dichloromethyl)-5- 
hydroxy-2(5H)-fiiranone (MX) in chlorinated drinking water in Finland in the early 1980’s 
caused great concern in the scientific and public health communities because MX was found 
to account for 20-60% of the mutagenicity in chlorinated drinking water. Later research 
showed that MX was also carcinogenic to rats (at a dose of 400 pg MX per kg body mass 
per day) (Komulainen et al., 1997). Other compounds similar to MX (referred to as MX- 
analogues), including ZMX, EMX, red-MX, ox-MX, mucochloric acid (MCA), and 
brominated forms of MX—BMX-1, BMX-2, BMX-3 (Figure 1) have also been identified in 
drinking water. 

Following the initial identification of MX in Finland (Kronberg and Vartiainen, 
1988), MX and MX-analogues were also detected in drinking waters from the United States, 
the United Kingdom, Australia, Canada, Spain, China and Japan, in levels ranging from 0.1 
to 90 ng/L (Andrews et al., 1990; Horth, 1990; Huixian et al., 1995; Meier et al., 1987; 
Simpson and Hayes, 1993; Simpson and Hayes, 1998; Smeds et al., 1995; Suzuki and 
Nakanishi, 1990; Wright et al., 2002). MX has been detected primarily in waters treated 
with chlorine, less so with the use of chlorine dioxide or chloramines, and very minimally in 
ozonated waters with post-chlorination (Holmbom and Kronberg, 1988). 


395 


The structural components responsible for the mutagenicity of MX are the CHCI 2 
and Cl substituents in a cis arrangement on a carbon-carbon double bond (Figure 1). The 
mutagenity of these substituents is enhanced by incorporation into the 5-hydroxy-2(5H)- 
furanone ring system or an open structure that can readily transform to this ring system 
under the conditions of mutagenic testing (Ishiguro et al., 1987). Therefore, when 
comparing the relative mutagenicities of the MX-analogues (Figure 1), EMX, ox-EMX and 
MCA are less mutagenic than the other MX-analogues. The mutagenicity of halogenated 
furanones is also enhanced by the presence of the C-5 hydroxyl group (Kronberg and 
Franzen, 1993), making red-MX less mutagenic than MX (LaLonde et ah, 1991). Bromine 
substitution with chlorine substituents can increase the toxicity of the compound, as found 
for THMs and the BMX-analogues (Bull, 1993; Ramos et ah, 2000). The bromine 
substituents originate from natural bromide ions found in many coastal ground and surface 
waters. 


While mutagenicity in Salmonella cannot be used to determine carcinogenicity in 
humans, MX is still considered a potential human carcinogen. Because MX and other 
analogues are highly mutagenic and there is very little occurrence data for them (particularly 
for the brominated-MX analogues), they received a high priority for inclusion in this 
Nationwide DBP Occurrence Study 

ANALYTICAL METHOD DEVELOPMENT 


Previous Methods 

Method development for the detection of MX in drinking water began in the 1980’s, 
at first catalyzed by Holmbom’s identification of MX in kraft chlorination effluent 
(Holmbom et ah, 1981). Soon after, Hemming et ah (1986) and Kronberg et ah (1988) 
detected MX in chlorinated drinking waters. The methods of Hemming et ah (1986) and 
Kronberg et ah (1988) became the key methods that were used to detect MX thereafter. 

The stability of MX is very sensitive to the pH of an aqueous solution. The ring 
form is predominant at low pH, but as the pH rises, the ring opens to ZMX, which 
tautomerizes to EMX, and at higher pH levels (above pH 8), degrades to smaller products 
(Kronberg and Christman, 1989, Figure 2). Hemming et ah (1986) and Kronberg et ah 
(1988) adjusted the pH to stabilize the ring form. The extraction method consisted of 
acidification of a large volume sample (10 L), concentration on a mixture of XAD resins, 
elution with ethyl acetate, and solvent reduction to dryness by rotary evaporation and 
nitrogen gas. Methylation of the hydroxyl group on the MX ring structure was achieved by 
heating with sulfuric acid in methanol (Figure 3). 


396 


Cl 



Cl Cl HO 



ZMX EMX 


Figure 2. MX degrades as pH increases. 


Cl Cl 





EMX EMXR 


Figure 3. Methylation of MX-analogues with sulfuric acid in methanol. 


Degradation 


pH >8 


397 










































Methylation converts the alcohol group on the MX ring to a methyl ether group, but 
the carboxylic acid groups of the open forms of MX (ZMX and EMX) are changed to esters, 
and the aldehyde groups to dimethyl acetal groups (Figure 3). Thus, to simplify naming the 
methylation products, they are all referred to as “esters,” i.e. MX becomes MXR. The 
esterified MX (MXR) was recovered by neutralization with sodium bicarbonate aqueous 
solution, and back-extraction into hexane. The reduced hexane extract (100 pL) was 
analyzed by capillary gas chromatographic (GC) separation and high resolution mass 
spectrometric detection (HRMS), with a detection limit of 2 ng/L MX. In some cases, 
researchers used high performance liquid chromatography (HPLC) prior to methylation to 
remove natural organic carbon contaminants (Kronberg et al., 1985a; Meier et ah, 1987). 

The HPLC separation involved first concentrating XAD extracts of drinking water to 
dryness by rotary evaporation, followed by soxhlet extraction with diethyl ether (Et 20 ), 
extraction with 2% sodium bicarbonate to remove strong acids, acidification of the aqueous 
phase to pH 2 with HC1, re-extraction with Et20, transfer to 30% methanol/water, separation 
into 2 mL fractions by a Cl8 semi-prep column using a 30-100% methanol/water gradient, 
followed by a 100% hold for 10 min, methylation of the weak acid fractions, and detection 
of MXR-analogues by GC/MS (Meier et ah, 1987). Other researchers applied a silica 
column clean-up step to the final hexane extract (Suzuki and Nakanishi, 1995), or multiple 
reaction monitoring during mass spectrometric detection (Simpson and Hayes, 1993) to 
isolate the MX-analogues from interfering co-contaminants such as natural organic matter 
(NOM). 

Identification of MX-analogues. The structure of MX was first determined by 
HRMS, UV and IR spectroscopy (Holmbom et ah, 1981). Padmapriya et ah (1985) reported 
the IR, UV, and ! H NMR spectra for MX and MXR, and the 13 C NMR spectrum for MX. 

No identification spectra have been previously published for ZMX. Kronberg et ah (1988) 
identified EMX by its ] H NMR and mass spectra, and EMXR by its mass spectrum. 
Kronberg et ah (1991) identified ox-EMX, ox-EMXR, ox-MXR and red-MX by their mass 
spectra. LaLonde et ah (1990) identified red-MX by its IR, 'H NMR, and 13 C NMR spectra, 
and MCA by its ] H NMR spectrum. Nawrocki et ah (2000) identified MCR by its mass 
spectrum. Lloveras et ah (2000) identified BMX-1, BMX-2, and BMX-3 by their ] H NMR, 
,3 C NMR and mass spectra. Peters (1991) identified BMXR-1, BMXR-2, and BMXR-3 by 
their mass spectra. 

Derivatization Efficiency. Kronberg et ah (1988) achieve derivatization of MX by 
addition of 2% sulfuric acid in methanol (^SCL/MeOH, Figure 3), heated at 70°C for 1 
hour. While the efficiency of this reaction has not been reported for the derivatization of 
MX, some researchers have compared the use of H 2 S 04 /Me 0 H to other derivatization 
agents. Diazomethane (CH 2 N 2 ) does not successfully methylate MX and its analogues 
(Kronberg et ah, 1991). Although H 2 SCVMeOH can adequately methylate MX, it cannot 
methylate the diacidic MX-analogues (ox-MX and ox-EMX). A 14% boron trifluoride 
methanol complex (BF 3 /MeOH) solution, heated at 70°C for 12 hours, was successfully 
applied to ox-MX and ox-EMX (Kanniganti et ah, 1992). Meier et ah (1987) claimed that 
the derivatization yield of EMX is related to the derivatization time (using Amberlite IR 120 
sulfonated polystyrene cation exchange resin in methanol, in a sealed tube, at 70°C for lb- 
18 hours). Huixian et ah (1995) compared the MXR yield from derivatization with 


398 


saturated BF 3 /MeOH to the method with 2% ^SCL/MeOH, and found that saturated 
BFs/MeOH was the more efficient derivatization agent regardless of reaction time (1-8 
hours at 95°C in water bath). Overall, BF 3 /MeOH has shown to be the best derivatization 
agent, with reaction time significantly affecting the product yield. 

Extraction Efficiency. Holmbom et al. (1984) evaluated a number of organic 
solvents and solid phases to extract MX from aqueous solutions; mutagenicity was 
measured as an indicator of MX recovery. Ethyl acetate (EtAc) completely extracted the 
mutagenicity (70-90%), while dichloromethane (50-70%) and pentane (<10%) recovered 
less of the mutagenicity. Rotary evaporation of EtAc extracts did not degrade the 
mutagenicity (even after 10 min at 40°C and 1.5 kPa). Adsorption of MX onto XAD-4 resin 
recovered similar amounts of mutagenicity as EtAc. Although MX can ionize in aqueous 
solution, anion-exchange solid phase materials are not appropriate for isolating MX from 
chlorinated aqueous samples. MX behaved as a neutral compound when applied to the 
anion exchange DEAE-Sepharose column due to the MX ring structure. 

Acidification prior to resin adsorption (XAD-2/8 resin adsorption/acetone elution) 
was essential for adequate recovery of MX in the protonated form (Figure 2) from spiked 
water samples and to maintain the stability of MX at low pH (Meier et al., 1987). MX was 
measured in terms of mutagenicity assays. XAD-2/8 recovery of mutagenicity from 
acidified (pH 2), chlorinated MX-spiked drinking water samples was only 55% effective. 
Subsequent extraction and HPLC isolation recovered only 18% of the remaining MX, 
resulting in an overall 10% MX recovery through XAD-2/8 adsorption, Et20 extraction, 
HPLC separation, and derivatization procedures. These percent recoveries were not taken 
into account when reporting MX concentrations, and no apparent method calibration 
solutions were analyzed to monitor recoveries at different MX concentrations. MX 
concentrations were determined relative to a derivatized MX standard by high resolution 
GC/MS analysis. Recoveries of MX from water samples buffered at higher pH levels (pH 
8) were 0-1%; the high pH favors MX in the ionized form and does not promote extraction 
from aqueous solution. Poor extraction recovery of MX from drinking water onto XAD 
resins was also attributed to complexation with chlorinated humic materials. When 
evaluated separately, the methyl-methacrylate polymer XAD-8 recovered more MX than the 
styrene-divinyl benzene copolymer XAD-2 (92 vs. 22 % MX recovery) from a fortified 
deionized water sample (20 L, 50 ng/L MX) at pH 2; MX recovery was measured by 
mutagenicity (Schenck et al., 1990). MX recovery was also significantly enhanced by 
reducing XAD-8 adsorption time; a total sample collection time of 25 hours recovered 92 % 
MX, whereas 56 hours recovered only 38 % MX (see stability section). 

The octanol-water partition coefficient, Ko W , is indicative of how much of an analyte 
is likely to partition out of water into a highly polar organic solvent. MX is fairly 
hydrophilic with a Ko W of 11.9 (mg/L octanol / mg/L water) at pH 2 (Holmbom et al., 1984). 
The Kq W value should be lower in neutral pH surface and drinking waters, and therefore MX 
is less susceptible to bioaccumulation in these waters. The Kq W of MX open (ZMX or 
EMX) in the neutral acid form was computed to be 1.16, using CLOGP, ver3.5 (Biobyte 
Inc., Pomona, CA) (DeMarini et al., 2000). The variability of these Ko W values is likely due 
to the difference between the ring and open forms of MX, and the pH considered. 


399 


Kronberg et al. (1991) used mucobromic acid (MBA, Figure 4) as an internal 
standard to assess recovery of MX-analogues through the derivatization process, by spiking 
MBA into the EtAc extract prior to derivatization (derivatization standard). However, MBA 
was determined to be an inappropriate surrogate standard (by spiking MBA into the original 
water sample prior to acidification and XAD adsorption) for the XAD/HPLC MX method 
(Simpson and Hayes, 1993), because MBA is more susceptible than MX to intermolecular 
hydrogen bonding with natural organics. The levels of MX recorded were corrected for 
recovery losses, based on separate MX method recovery experiments (average 10% 
recovery, consistent with Meier et al. 1987). Higher levels of total organic carbon (TOC) in 
drinking water have been associated with lower recovery of MX (Meier et al. 1987). The 
high Kow (11.9 mg/mg) for MX, may indicate the likelihood that MX would strongly 
associate with NOM as a highly polar solvent, and not be easily extracted by XAD. The 
major loss of MX was seen in the HPLC fractionation steps (average 60% recovery in this 
step, Simpson and Hayes, 1993), but these steps are only necessary in high TOC waters. 
Multiple reaction monitoring (MRM) by mass spectrometry was investigated as an 
alternative method to HPLC for removal background natural organic interferences, and it 
showed some promise (Simpson and Hayes, 1993). MRM eliminates interference from co¬ 
extracting compounds by monitoring compound-specific metastable transitions between 
selected parent and daughter ions of the target analyte. 


Br Br 





MBA open 


Figure 4. Mucobromic acid (MBA) isomers. 


Stability of MX-Analogues. MX hydrolysis, isomerization, and decomposition 
processes in aqueous solution are strongly dependent on pH (Holmbom et al., 1989). MX is 
stable at pH 2 but starts to degrade at pH 4 and above. Beyond pH 6.5, the water solubility 
of MX increases rapidly, due to ring opening and dissociation (tautomerization), as 
determined by extraction of aqueous MX solutions with ethyl acetate at different pH values 
(Holmbom et al., 1984). The degradation of MX at pH 5-7 correlates with the formation of 
EMX (Simpson and Hayes, 1993). However, EMX also degrades over time at neutral or 
alkaline pH (Holmbom and Kronberg, 1988). When acidified to pH 2, EMX completely 
converts to MX. The BMX-analogues also show tautomerization, degrading over time (48 
hours) from the ring forms to the open forms and finally to degradation products, as 
measured in a pH 7.4 phosphate-buffered aqueous solution by HPLC/UV (Ramos et al., 
2000), similar to MX in Figure 2. 


400 







Meier et al. (1987) measured the mutagenic activity of MX spiked distilled water 
samples at 4°C. It was constant at pH 2, 4, and 8 over 14 days, but declined to 30% at pH 6 
after 14 days. At 23°C, the order of stability was pH 2 > pH 4 > pH 8 > pH 6, where pH 2 
was constant. The loss of activity in pH 4-8 followed first-order decay kinetics. ZMX 
occurred in MX solutions buffered at pH 6, but less at pH 8 (stored for 7 days at 23°C). The 
pK a value of MX was determined to be 5.3 by NMR spectroscopy (Streicher, 1987). 
However, the pK a of MX open (ZMX or EMX) was computed to be 1.85, using the SPARC 
method (DeMarini et al., 2000). The variability of these two pK a values is likely due to the 
difference between the ring and open forms of MX. 

Meier et al (1987) determined the half-lives of MX in distilled water at 23°C to be 
12.9 days at pH 4, 4.6 days at pH 8, and 2.3 days at pH 6, by measuring loss in 
mutagenicity. When MX was spiked into tap water samples buffered at pH 6 and 8, stored 
at 23°C, the same losses in mutagenicity were seen as those in distilled water. This work 
was confirmed by measuring MX concentration at pH 2-9 in MX spiked Milli-Q water by 
HPLC/UV analysis (Simpson and Hayes, 1993). Simpson and Hayes (1993) recovered 95% 
of the original MX in pH 2 Milli-Q water stored at 20°C after 14 days. At the same 
temperature, the half-life of MX at pH 8 (11.3 days) was much longer than that for pH 6 
(5.4 days). However, at 23°C, the half-life of MX at pH 8 was 4.6 days. This agrees with 
rates of hydrolysis at pH 7.0 measured by Croue and Reckhow (1989) at 20°C, k = 0.9±0.5 x 
10' 6 s' 1 ( -0.07 days' 1 ) and tj /2 — 8.9 days. 

MX has been shown to degrade in the presence of increasing concentrations of 
chlorine (10-100 mg/L CI 2 ), buffered at pH 8 (Schenck et al., 1990; Simpson and Hayes, 
1993). The second order rate constant for MX degradation by chlorine was estimated to be 
32.3 L mol' 1 min' 1 , based on the reaction rate over the first 10 min and initial concentrations 
of 20 mg/L MX and 40-120 mg/L CI 2 (Schenck et al., 1990). MX degradation was also 
observed at lower residual chlorine concentrations (0.5-3 mg/L CI 2 ) that might be practical 
levels found in drinking water treatment plant effluents. Chlorine and MX reacted at about 
a 5:1 molar ratio, and the reaction was complete within 1 day (Schenck et al., 1990). MX 
can be converted to EMX, ox-MX and ox-EMX in the presence of chlorine (Simpson and 
Hayes, 1993). However, in the presence of chloramine (10-100 mg/L NH 2 CI), MX converts 
to only EMX, due to the fact that chloramine is not as strong of an oxidizing agent as 
chlorine. EMX, ox-MX and ox-EMX were qualitatively identified as disinfection by¬ 
products, but their levels were not quantified in these studies. 

Due to the MX degradation by chlorine, some researchers tried to quench the 
residual chlorine prior to MX analysis. Simpson and Hayes (1993) identified L-ascorbic 
acid (Figure 5, note similar furanone structure to MX) as the best quenching agent for MX, 
because nucleophiles in other quenching agents (e.g., sodium thiosulfate or sodium sulfite) 
destroy MX by removing chlorine atoms (Croue and Reckhow, 1989). The rates of 
decomposition of MX significantly increase in the presence of sulfite (100 pM) at 20°C, k = 
22±3 x 10' 6 s' 1 and tj/ 2 ~ 8.7 hours (Croue and Reckhow, 1989). Suzuki and Nakanishi 
(1990) suggest that quenching residual chlorine is unnecessary; after acidification, their 
samples were purged with nitrogen gas and the residual chlorine was reduced to 0.2 mg/L; 


401 


no difference in MX concentration was observed between purged and non-purged samples. 
However, considering the MX degradation by chlorine observed by Schenck et al. (1990), 
quenching of residual chlorine is necessary for a 0.3 mg/L chlorine residual and above. 


HO OH 



Figure 5. Structure of ascorbic acid (Vitamin C). 

Summary of Current Methods for Analysis of MX-Analogues in Drinking Water 

MX, ZMX, EMX, and MCA. The method of Kronberg et al. (1991) for extraction of 
MX, ZMX, EMX, and MCA from aqueous solutions involves first acidifying the solution to 
pH 2, passing the solution through a mixture of XAD-4 and XAD-8 resins (1:1), and eluting 
the adsorbed compounds with ethyl acetate (EtAc). However, liquid-liquid extraction has 
met with some success. By extracting 250 mL of a solution with successive 40, 20, and 20 
mL volumes of diethyl ether, 77% of MX was recovered (Kanniganti et al., 1992). MBA 
was added to the EtAc extract as the derivatization standard. The EtAc extract was blown 
down to dryness, derivatized with 250 pL of 2% HiSCU/MeOH at 70°C for 1 hour, 
neutralized with 2% NaHCCVdeionized water (DIW), and extracted twice with 250 pL of 
hexane. The hexane extract was then concentrated down to 100 pL and decafluorobiphenyl 
was added as an internal standard. The extract was analyzed by gas chromatography on a 
DB-1 column (30m), with a temperature program of 110°C for 3 min, 6°C/min to 165°C, and 
the resolved compounds detected by HRMS, single ion monitoring mode (Kronberg et al., 
1991). The extract can also be separated on a DB-5 column (30-m x 0.25 mm ID x 0.25 pm 
film thickness), using the temperature program 50°C for 1 min, 2.5°C/min to 150°C, 5°C/min 
to 300°C (Kanniganti et al., 1992). 

red-MX. The method of Kronberg et al. (1991) for extraction of red-MX from 
aqueous solutions involves first acidifying the solution to pH 2, passing the solution through 
a mixture of XAD-4 and XAD-8 resins (1:1), and eluting the adsorbed compounds with 
ethyl acetate. Since the EtAc extract did not require derivatization, 2,3-dibromo-2(5H)- 
furanone (red-MBA) was added as an internal standard, and the extract was reduced to 100 
pL with nitrogen gas. The EtAc extract was separated by gas chromatography on a DB-1 
column (30 m), with a temperature program of 110°C for 3 min, 6°C/min to 165°C. Red- 
MX is detected by HRMS based on retention time and most abundant ions: m/z 165 and 167 
for (M-Cl) + , 171 and 173 for(M-CHO) + . 

ox-MX and ox-EMX. The method of Kronberg et al. (1991) for extraction of ox- 
MX and ox-EMX from aqueous solution involves first acidifying the solution to pH 2, 
passing the solution through a mixture of XAD-4 and XAD-8 resins (1:1), and eluting the 


402 




adsorbed compounds with ethyl acetate. MBA was added to the EtAc extract as the 
derivatization standard. The EtAc extract was blown down to dryness, derivatized with 250 
pL of 12% BF 3 /MeOH at 100°C for 12 hours, neutralized with 2% NaHCCVDIW, and 
extracted twice with 250 pL of hexane. The hexane extract was then concentrated down to 
100 pL and decafluorobiphenyl added as an internal standard. The extract was analyzed by 
gas chromatography on a DB-5 column (60 m), with a temperature program of 160°C for 3 
min, 6°C/min to 190°C. Ox-EMX elutes immediately prior to ox-MX using GC/MS 
(HP5890 GC/VG 70-250 SEQ mass spectrometer, resolving power 1000). The LLE method 
using diethyl ether has also been applied successfully to these compounds (Kanniganti et al., 
1992). 


BMX-Analogues. The method for analysis of BMX-1, BMX-2, and BMX-3 is very 
similar to that of MX (Suzuki and Nakanishi, 1995). The BMX-analogues were measured 
in Japanese drinking waters by acidifying 10 L samples to pH 2, passing them through 50 
mL XAD-8 resins, eluting with 150 mL EtAc, and concentrating down to 5 mL by rotary 
evaporation at 40°C. Three mL of this extract was spiked with 100 ng MBA as the 
derivatization standard, and evaporated to dryness with nitrogen (N 2 ) gas. The residue was 
methylated with 250 pL of 2% ^SOVMeOH for 1 hour at 70°C, neutralized by 500 pL of 
2% NaHCCVDIW, and extracted twice with 500 pL hexane. The hexane extract was then 
passed through a 500 mg Sep-Pak silica column, eluted with 1 mL hexane and 5 mL ethyl 
acetate:hexane (1:7), and only the last 4 mL fraction was collected and concentrated to 100 
pL with N 2 . Separation was achieved using a 30-m x 0.25 mm ID DB-5MS GC column, 
injection temperature 160°C, temperature program 50°C for 2 min, 50-120°C at 40°C/min, 
120°C for 2 min, 120-135°C at 2°C/min, 135-180°C at 6°C/min, 180°C for 5 min. The 
components were detected by HRMS using a VG Autospec-Ultima mass spectrometer. 
Spike recoveries ranged from 71 to 122%. 

The BMX compounds are susceptible to thermal degradation in the injection port of 
a GC. An injection temperature of 160°C produced a larger BMX-3 signal (HRMS) than 
200°C, in a calibration range of 0-1000 pg/pL. Calibration solutions were made from 
standards of the esterified BMX compounds. Detection limits were also dependent on 
compound stability in the GC injection port. The detection limit for MX was 0.1 ng/L, 
whereas BMX-3 was 0.5 ng/L, using a 60,000:1 concentration factor. BMX-1 and BMX-2 
showed intermediate thermal degradation (and intermediate detection limits) to MX and 
BMX-3. 


Opportunities for Improvement of Existing Methods. A unified method needs to be 
developed for the analysis of all MX-analogues in drinking water in a single extract, which 
accounts for sample preservation and recovery of MX-analogues through each processing 
step. Routine analysis by GC-ECD instead of high resolution GC/MS would make the 
method more amenable for environmental and water treatment laboratories in the United 
States. Evaluation of quenching agents for residual chlorine and biocides to prevent 
microbial regrowth would improve sample preservation and prevent degradation of MX- 
analogues. Evaluating percent recoveries from each processing step based on detection of 
individual halogenated furanones, rather than by mutagenicity, would also prove more 


403 


valuable in the development of an analytical method for the detection of MX-analogues in 
drinking water. 

New Method Development 

Identification and Quantification of Standards. Development of a method for the 
analysis of MX-analogues (Figure 1) in drinking water began by first identifying and 
quantifying the compounds in synthesized and commercially available standards. The only 
commercially available MX-analogues were MX, mucochloric acid (MCA), and 
mucobromic acid (MBA, surrogate standard), from Sigma-Aldrich (St. Louis, MO). The 
other components were provided in small mg quantities from the labs of individual 
researchers. Leif Kronberg (Abo Akademi, Finland) synthesized EMX (75% purity) and 
ox-EMX (Kronberg et al., 1991). Ramiah Sangaiah (UNC) synthesized MX, red-MX, and 
ox-MX (Kronberg et ah, 1991; Padmapriya et ah, 1985). Angel Messeguer (CSIC, Spain) 
synthesized BMX-1, BMX-2, and BMX-3 (Lloveras et ah, 2000). Starting with MX 
(Sigma-Aldrich), the identities and purities of the compounds were confirmed by H and C 
nuclear magnetic resonance, electron ionization and chemical ionization mass spectrometry. 

Qualitative and Quantitative NMR. Milligram quantities of MX-analogues (Figure 
1 + MBA) were dissolved in deuterated methanol (Aldrich, 99.8 atom %D), and transferred 
to 5 mm NMR tubes to a height of 60 mm (~1 mL). All spectra were obtained on an Inova 
500 MHz NMR instrument. 1,4-Dioxane (Aldrich, 99.8%) was chosen as the internal 
standard due to its volatility, and ease of removal from the MX analogues after NMR 
analysis. 1,4-Dioxane interferes with only one chemical shift in MXR. Carbon-13 NMR 
spectra were obtained for four MX analogues in decoupling mode. 

Purity Assay Calculations. Thirty pL of 1,4-Dioxane (density: 1.0337 g/mL) was 
spiked into 1 mL of deuterated methanol, for a concentration of 30.1 mg/mL in the primary 
stock solution. Five pL of the primary stock solution was spiked into each NMR sample, 
which is equivalent to 150.5 pg 1,4-dioxane per sample. The quantitative ] H NMR 
spectrum of BMX-3 revealed a dioxane peak at 5 3.65 ppm with a peak area equivalent to 8 
H's. The peak area of dioxane was then set to 8.00, so that all other areas would be 
calculated relative to dioxane. The Ring H of BMX-3 at 5 6.35 ppm is equivalent to 1 H 
with a peak area of 7.03. The weight of BMX-3 in the NMR tube was calculated by 
Equation 1. 


W = W x 

VV unk VV std A 


N 


std 


N 


M unk ^ A U nk 


unk 


M 


std 


A 


std 


A = peak area 
N = number of protons 
M = molecular weight 
W = weight present. 


(Equation 1, Willard et al., 1988) where 


For BMX-3, 
W 


BMX-3 


1CAC 8H 350.79g/mol 7.03 , 

150.5pgx -x-x-= 4.21 mgBMX-3 

1H 88.11 g/mol 8 


404 








The solution in the NMR tube was then transferred to a tared 4 mL amber vial and 
dried under gentle flow of nitrogen gas. When the deuterated methanol evaporated to 
dryness, the vial was placed in a vacuum manifold to ensure removal of the solvent. The 
vial was then weighed on a microscale and the weight of the NMR sample by difference was 
5.5 mg. Therefore, BMX-3 is 76% pure as measured by proton NMR. The remaining NMR 
samples were assessed for purity in the same manner (Table 1). The ox-MX and red-MX 
standards were prepared without addition of the internal standard dioxane. However, they 
could still be quantified relative to residual MX remaining in the standard from the synthesis 
reaction. Ox-MX was found to be 17% pure relative to MX, and red-MX was 88 % pure 
relative to MX, by 'H NMR. 


Table 1. Purity of Si 

tandards by Quantitative NMR 

Compound 

Calculated Weight 
(mg) 

Original Weight 

(mg) 

Percent Purity 

MX (Sigma) 

3.46 

5.2 

66% 

MX ester 

1.58 

2.64 

60% 

BMX-1 

0.76 

4.0 

19% 

BMX-2 

1.06 

4.0 

27% 

BMX-3 

4.21 

5.5 

76% 

MCA 

4.98 

6.0 

83% 

MBA 

6.65 

10.4 

63% 

Ox-MX 



17% 

Red-MX 



88 % 


The brominated MX-analogues (BMX-1, BMX-2, BMX-3) were synthesized 
overseas and arrived as one neat 10 mg mixture of BMX-1 and BMX-2, as well as one neat 
5 mg BMX-3. Therefore, BMX-1 and BMX-2 had to be separated by high performance 
liquid chromatographic (HPLC) fractionation (Lloveras et al., 2000). The 10-mg mixture of 
BMX-1 and BMX-2 was dissolved in 1.5 mL of deuterated methanol (CD 3 OD) and the 'H 
NMR spectrum was obtained by an Inova 500 MHz instrument. The NMR sample was 
transferred from the NMR tube to a 4 mL amber vial with two successive washes with 
regular methanol (Burdick & Jackson THM-free methanol). The methanol was evaporated 
under gentle flow of nitrogen gas. The residue was then diluted to 100 pL and transferred to 
an HPLC vial with a 350 pL insert. Twenty-five pL aliquots of the BMX mixture were 
injected onto the Waters HPLC system. The course of the separation was monitored at 
>.=254 on a photodiode-array detector, using 25:75 acetonitrile (ACN): 0.05 M buffer 
HCOOH:Et 3 N pH 3.2 as the eluent system, at a flow rate of 2.5 mL/min (Beckman 
Ultrasphere ODS 5 pm x 10 mm x 25 cm). The compounds eluted in the order of, first, an 
unknown, second, BMX-1, and third, BMX-2. The latter two peak eluates were collected 
with an automated fraction collector. 

Each 35-mL fraction was separately extracted in a 125 mL separatory funnel with 
two 50 mL aliquots of Ethyl Acetate (Mallinckrodt AR). The aqueous layer was removed 


405 


















(and stored in the refrigerator in case re-extraction was needed). The organic layer was 
extracted with 40 mL of brine (DIW saturated with NaCl, Mallinckrodt AR), and the 
aqueous layer was removed and disposed. The organic layer was dried over a funnel filled 
with a glass wool plug and ample sodium sulfate (Na 2 S 04 , EM Science, Granular), and 
collected in a round bottom flask. The ~100 mL organic layer was dried down to 1 mL with 
a rotary evaporator. The remaining 1 mL was loaded onto a preparatory thin-layer- 
chromatography (TLC) silica plate with a Pasteur pipette and developed for 1 hour with a 
mobile phase of 1:1 ethyl acetate and hexane (Mallinckrodt AR) in a glass development 
chamber. BMX-1 gave an Rf value of 0.51, and the Rf of BMX-2 was 0.24. 


406 


Compound Identification Confirmation by Direct Probe Mass Spectrometry. The 
electron ionization mass spectra of MX and red-MX were acquired and confirmed by 
literature spectra (Kronberg et al., 1991; LaLonde et al., 1990; Padmapriya et al., 1985). 
The mass spectrum of ox-MX was not previously published, so it is included below (Figure 
6 ). It was found to contain significant contamination from MX (Figure 6, Table 2). 



Figure 6. Background-subtracted direct insertion probe El mass spectrum of 
synthesized ox-MX (1.81 mg/mL, molecular ion = 232,17% pure by proton NMR). 


Table 2. Ox-MX fragmentation 


m/z 

Fragment ion 

187 

(M-C0 2 H) + 

133 

MX contaminant 

107 

C 3 HC1 2 + 

73 

C 3 H 2 Cf 


407 



















































































































Derivatization of MX-Analogues for GC-ECD and GC/MS Detection. Gas 
chromatography with electron capture (GC-ECD) and mass spectrometric (GC/MS) 
detection were chosen as the ideal separation and detection methods for the analysis of MX- 
analogues because these types of instrumentation are widely used by environmental and 
water utility laboratories across the United States. However, the majority of the MX- 
analogues contain one or more hydroxyl groups that can react with unprotected silanol 
groups on the solid phases of gas chromatographic open tubular columns. Therefore, a 
methylating agent was chosen to protect the hydroxyl groups of the MX-analogues and 
allow separation of the MX-analogues on a GC column. The boron-trifluoride methanol 
complex (BF 3 /MeOH, Sigma) was chosen in order to effectively methylate all of the MX- 
analogues; this is the only methylating agent suitable for ox-MX (Kronberg et al., 1991). 

The limiting concentration of BF 3 /MeOH was unclear from previous work 
(Kanniganti et al., 1992), and was evaluated by adding increasing volumes of 14% 
BF 3 /MeOH to a 1 mL solution of MX in methanol (25 pg/L MX/MeOH) (THM-free 
methanol, Burdick & Jackson). By varying the amount of BF 3 /MeOH added, the 
concentration changed from 7% BF 3 /MeOH with a 1 mL addition, to 9% with 2 mL, and 
10.5% with 3 mL. Each mixture was sealed with a Teflon-lined, open-top screw cap and 
heated in a heating block at 70°C (just above the boiling point of methanol, 67°C, to 
encourage reflux) for 16 hours (Ball, 1998, personal communication). To halt the 
derivatization reaction after 16 hours, a saturated solution of sodium bicarbonate in 
deionized water (10% NaHCCE) was added until the pH approached neutral (pH 7). The 
methylated MX in the neutral solution was then back-extracted with 1 mL of hexane (Ultra- 
Resi grade 95%, J.T. Baker). The neutral pH of the aqueous fraction ensured that any 
underivatized MX would remain ionized and dissolved in water, and would not be extracted 
by hexane. The saturated salt solution (10% NaHCC^), used to neutralize the BF 3 /MeOH, 
has been shown to improve extraction recovery of the esters into hexane (Metcalfe et al., 
1966). 


When analyzed by GC-ECD on a DB-1701 (30-m x 0.25 mm ID x 0.25 pm film 
thickness) fused-silica column, the 9% BF 3 /MeOH solution gave the largest area response 
for MXR. Thereafter, a volume ratio of 2:1 BF 3 /MeOH to MX/MeOH was utilized for the 
derivatization step. The final hexane extract was separated on a DB-1701 column with a 
temperature program of 50°C for 1 min, and 2.5°C/min to 250°C, revealing a retention time 
of 46.7 min for MXR. 

Additional MX-analogues were derivatized with BF 3 /MeOH, as outlined above, and 
analyzed by gas chromatography-ion trap mass spectrometry using both electron ionization 
(El) (example in Figure 7, Table 3, ox-MXR) and chemical ionization (Cl) modes. The total 
ion chromatogram and mass spectra obtained for the esterified mucochloric acid revealed 
two products, MCR ring form and MCR open form (the methylated 2,3-dichloro-4- 
oxobutenedioic acid) (Kanniganti et al., 1992; Nawrocki et al., 2000). The two peaks eluted 
at 12.2 and 20.5 min, on the DB-5 column, with a temperature program of 60°C for 1 min, 
2.5°C/min to 250°C, and 250°C for 5 min; injection temperature of 150°C. 


408 



ion = 260, R t =26.43 min); agrees with mass spectrum of methylated ox-MX found by 
Kronberg et al. (1991). 


Table 3. Ox-MXR fragmentation 


ttl/z 

Fragment ion 

229 

(M-OCH 3 ) + 

228 

(M-CH 3 OH) + 

225 

(M-C1) + 

201 

(M-C0 2 CH 3 ) + 

197 

(M-C1-C 2 H 4 ) + 

109 

c 2 h 2 o 3 ci + 

107 

c 3 hci 2 + 

79 

co 2 cf 


The esterified mucobromic acid also contained two peaks (MBR ring and MBR open 
forms) (Backlund et al., 1988; Kronberg et al., 1988; Nawrocki et al., 2000), eluting at 19.17 
and 25.73 min. This was also the case for the esterified brominated MX-analogues (BMXR- 
1 at 25.98 min, BEMXR-1 at 30.70 min, BMXR-2 at 30.14 min, BEMXR-2 at 34.45 min, 
BMXR-3 at 34.26 min, BEMXR-3 at 37.59 min). The BMX compounds synthesized by 
Angel Messenguer were not pure. Each one contained three components: an unknown 
peak, the ring form (BMXR) and the open form (BEMXR). Identities of these esters were 
confirmed by spectra in the Ph.D. thesis of Peters (1991). 

By GC/MS peak area, red-MX was 66% pure relative to MXR, eluting at 19.08 min, 
and ox-MXR was 28% pure relative to MXR (Figure 8, Table 4), eluting at 26.43 min. The 
detector response for red-MX following derivatization was considerably lower due to losses 
during back-extraction into hexane. Red-MX does not require methylation because it lacks 


409 







































the hydroxyl group present on the MX ring. The identity of ox-MXR was confirmed by 
GC/MS (Kanniganti et al., 1992; Kronberg et al., 1991). The mass spectrum of ox-EMXR 
could not be obtained due to the small amount of available material and detection limit 
constraints on the Saturn II mass spectrometer. The percent purities of the MXR-analogues 
are given in Table 5, based on GC/MS peak area. 

In order to isolate and quantify EMX, the method required further manipulation. 

MX was shown previously to isomerize to EMX above pH 4 (Holmbom et ah, 1984). 
Therefore, a pH 6 phosphate-buffered aqueous solution containing MX was monitored over 
time for production of EMX. Aliquots (1 mL) of this solution were taken at time increments 
from 10 min to 24 hours, and extracted with methyl tertiary -butyl ether (MtBE, OmniSolv 
grade, EM Science, 1 mL). These MtBE extracts were derivatized with BFs/MeOH, and 
extracted with hexane, as outlined above. The hexane extracts were analyzed by GC-ECD 
and GC/Ion Trap MS on a DB-5 (30-m x 0.25 mm ID x 0.25 pm film thickness, J&W 
Scientific/Agilent, Folsom, CA) column using a temperature program of 60°C for 1 min, 
2.5°C/min to 150°C, and held at 150°C, to encompass the eluting compounds’ retention 
times. Each of the hexane extracts contained three distinct peaks: MXR at 22.85 min, 
ZMXR at 28.17 min, and EMXR at 29.34 min, as identified by GC/MS (Kronberg et ah, 
1988). The ratio of MXR to ZMXR to EMXR was 34:15:1, and did not change over the 
time tested (10 min to 24 hours), as measured by GC-ECD. Therefore, the MX->EMX 
reaction was not observed at pH 6, unless, of course, the reaction completes in less than 10 
min. In subsequent investigations, quantification of EMX was determined against a 2% 
presence in the MX standard (Table 5). Similarly, quantification of ZMX was determined 
against a 31% presence in the MX standard. 

Derivatization Reaction Time 

The optimum derivatization time for MX in the 1-8 hour range was 4 hours with a 
65% yield. Aliquots (1 mL) of MX solution (10 pg/mL MX/MeOH) were derivatized with 
2 mL of 14%BF3/MeOH at 70°C for 1, 2, 3, 4, 5, 6, 7, and 8 hours. These results enabled 
the derivatization time of MX to be reduced from 16 to 4 hours. Then the derivatization 
time was evaluated for a mixture of other MX-analogues, for 1-8 hours (Onstad and 
Weinberg, 2001). The mixture contained 250 ng of each MX-analogue dissolved in 
methanol. Most of the compounds (MX, MCA, MBA, BMX-1, BMX-2, and BMX-3) 
approached a threshold derivatization efficiency after 3 hours (see Figure 9), with the 
exception of ox-MX, which will not completely derivatize even after 19 hours. Previous 
researchers used a derivatization time of 10-16 hours at 70-100°C in combination with a 
boron trifluoride methanol complex (Ball, 1998, personal communication; Kanniganti et al., 
1992; Kronberg et al., 1991). A derivatization time of 4 hours was chosen for the 
compounds overall. 


410 


O perator: G O 

Date: 10/4/1999 4:30 PM 


Chromatogram Plot 

File: e:\10049905.ms 
Sample: 1.81 MG OX-MX 

Scan Range: 1 - 4200 Time Range: 0.01 - 42.00 min. 
Sample Notes: 1.81 MG OX-MX 



Figure 8. Total ion chromatogram for methylated ox-MX (1.81 mg/mL), with the MX, 
ZMX and EMX esters in the mixture. 


Table 4. Percent Purity of ox-MXR standard 


Compound 

% TIC 

% Area 

MXR 

52% 

58% 

Ox-MXR 

32% 

28% 

ZMXR 

14% 

12 % 

EMXR 

2 % 

2 % 


411 






































Table 5. Purity of Ester Standards by GC/Ion Trap MS 


Compound 

Percent purity with respect to components (by area) 

MXR 

67% MXR, 31% ZMXR, 2% EMXR 

Ox-MXR 

28% MXR, 58% ox-MXR, 12% ZMXR, 2% EMXR 

Red-MX 

66 % red-MX, 29% MXR, 8% ZMXR 

BMXR-1 

31% UNK BMX-1, 9% BMXR-1 A, 35% BMXR-1B, 25% BEMXR-1 

BMXR-2 

61% UNK BMX-2, 23% BMXR-2, 16% BEMXR-2 

BMXR-3 

41% UNK BMX-3, 41% BMXR-3, 18% BEMXR-3 

MCR 

18% MCR ring, 82% MCR open 

MBR 

27% MBR ring, 73% MBR open 


60 



Derivatization Time (hours) 


■ MCR ring 
■MCR open 
■ZMXR 
•EMXR 
■MBR ring 

■ MBR open 
ox-MXR 


Figure 9. Derivatization of MX-analogues with boron trifluoride/methanol. 


412 




































Back-Extraction of the MXR-analogues into Hexane 

The final step in the analysis was evaluated to determine the recovery of the 
esterified forms of the MX-analogues during back-extraction from bicarbonate solution to 
hexane (Onstad and Weinberg, 2001). Synthesized MXR-analogues were dissolved in 
methanol and spiked into an aqueous sodium bicarbonate solution. Results were attainable 
for only four of the MX-analogues (Table 6) (red-MX was not extractable by hexane). The 
equation used to calculate the partition coefficients (Kd) for MXR-analogues between 
sodium bicarbonate solution and hexane follows (Equation 2): 



(Eqn.2) 


where Kd = partition coefficient at equilibrium 

C s = concentration of MXR-analogue in hexane (ng/mL) 

C a = concentration of MXR-analogue in sodium bicarbonate solution (ng/mL) 


MXR and MCR open exhibited the best recoveries by hexane extraction, although 
only 60% on average (E in Equation 3 and Table 6). Hexane only recovered 7% of the 
original ox-MXR. Red-MX, when included in this mixture, cannot be recovered at all by 
hexane. Therefore, other extraction processes are being investigated for red-MX that do not 
require derivatization prior to GC-ECD analysis. One possibility could be to analyze the 
MtBE extract directly by GC-ECD, after addition of the internal standard (Kronberg et al., 
1991). The fraction of the MXR-analogue extracted (E) was calculated using the following 
equation: 



(Eqn.3) 


where E = the fraction of MXR-analogue extracted 
V s = volume of hexane (mL) 

V a = volume of sodium bicarbonate solution (mL) 


The "n for 75%" indicates the number of extractions ( n ) needed to recover 75% of 
each MXR-analogue. This value is calculated using the following equation (Equation 4), 
setting E equal to 0.75: 


log(l - E) 



where V = V s /V a 


(Eqn. 4) 


By adding another hexane extraction and combining the two hexane extracts, MXR 
and MCR open can be more efficiently recovered from the bicarbonate solution. Two 
hexane extractions are consistent with previous methods for the esterified MX-analogues 
(Hemming et al., 1986; Kronberg et al., 1991). Recovery of the brominated MXR- 
analogues is still under investigation. 


413 





Table 6. Partitioning of MXR-analogues into Hexane 


Compounds 

MXR 

MCR 

open 

ox-MXR 

red-MX 

Kd 

4.75 

8.58 

0.29 

0.00 

E (Recovery) 

54% 

68 % 

7% 

0 % 

n for 75% 

1.77 

1.21 

19.95 

NA 


NA: not applicable 


Instrument Detection Limits and Gas Chromatographic Separation 

A mixture of esterified MX-analogues was separated on a DB-5 column (60-m, 0.25 
mm ID, 0.25 pm film thickness) (Figure 10) with a mild temperature gradient (2.5°C/min) 
from 105 to 195°C, followed by a high temperature gradient (20°C/min) up to 250°C 
(Onstad et al., 2000). A shorter column length (30 m) of the same phase did not allow 
separation between red-MX and the open form of mucochloric acid ester (MCR open). 
Coelution was observed between MX and an unknown component in the standard of BMX- 
2 (BMX-2 UNK). However, this coelution does not preclude detection of MX, because MX 
can be quantified by the ZMX peak (#14, Table 7), although, with greater variability. Two 
peaks are present for BMX-1 ring , which could be due to the presence of diastereomers, as 
the ion trap mass spectra appear identical, and the chromatographic retention times are 
close. Twelve components in the gas chromatogram are listed in Table 7, in addition to red- 
MX, the three BMX unknowns and the internal and surrogate standards. Use of an HP 6890 
GC fitted with a micro electron capture detector (p-ECD) enabled instrument detection 
limits of 1 pg/pL for MXR, MCR, ox-MXR, and red-MX; 16 pg/pL for BMXR-1 and 
BMXR-3; and 25 pg/pL for BMXR-2, in the final hexane extract. 



Figure 10. GC-ECD chromatogram of 7 MX-analogues and isomers at 20 pg/pL. 


414 






































Table 7. Peak identification in GC-ECD trace 


Elution 

Order 

Retention Time 

Compound 

1 

10.022 

3-Bromochlorobenzene (internal standard, IS) 

2 

11.597 

Mucochloric ester (ring) (MCR ring) 

3 

17.372 

unknown component of BMX-1 standard (BMX-1 
UNK) 

4 

17.758 

Mucochloric ester (open) (MCR open) 

5 

18.159 

Red-MX 

6 

18.543 

Mucobromic ester (ring) (surrogate standard, MBR 
ring) 

7 

21.143 

unknown component of BMX-2 standard (BMX-2 
UNK) 

8 

21.143 

MX ester (ring) (MXR) 

9 

24.122 

Ox-MX ester (ox-MXR) 

10 

24.423 

Mucobromic ester (open) (surrogate standard, MBR 
open) 

11 

25.087 

unknown component of BMX-3 standard (BMX-3 
UNK) 

12 

25.158 

BMX-1 ester (ring) (BMXR-1A) 

13 

25.399 

BMX-1 ester (ring) (BMXR-1B) 

14 

25.998 

ZMX ester (ZMXR), an open form of MXR 

15 

27.016 

EMX ester (EMXR), an open form of MXR 

16 

29.428 

BMX-2 ester (ring) (BMXR-2) 

17 

29.719 

BMX-1 ester (open) (BEMXR-1) 

18 

33.391 

BMX-2 ester (open) (BEMXR-2) 

19 

33.461 

BMX-3 ester (ring) (BMXR-3) 

20 

36.641 

BMX-3 ester (open) (BEMXR-3) 


MX recoveries by other organic solvents, ethyl acetate (EtAc, EM Science, 
OmniSolv grade) and hexane (Burdick & Jackson, for THM analysis), were compared to 
MtBE using the 10:2 aqueous solution (100 ng/mL MX/DIW) to organic solvent extraction 
ratio, and a single extraction. Ethyl acetate (94% recovery) recovered similar amounts of 
MX as MtBE (83%), while hexane (7%) was relatively unsuccessful at recovering MX from 
the aqueous solution. The high recoveries of MX (83% MX with MtBE vs. 58% in previous 
experiment) can be explained by the doubling of the derivatization solvent ratio to LLE 
extraction solvent (2 mL of 14%BF 3 /MeOH to 500 pL of LLE solvent). Thereafter, the 
LLE extraction solvent was reduced to 500 pL with nitrogen (N 2 ) gas prior to addition of the 
derivatization agent. MtBE was chosen as the better extracting solvent over EtAc, because 
MtBE can be obtained from manufacturers at a higher level of purity; the GC-ECD trace of 
EtAc contained several contaminant peaks in the vicinity of the MXR elution time. 

Liquid-liquid extraction was applied to other MX-analogues, and MtBE was 
evaluated for recovery of MCA, red-MX, MBA, MX and ox-MX from an aqueous solution 
(1 ng/mL each in DIW), using the 20:4 extraction ratio, and triplicate extractions. MtBE 
recovers 40-90% of the MX-analogues (Table 8). This translates to a detection limit of 4-9 


415 


























pg/ja.L on column, or 200-450 ng/L in a 20 mL drinking water sample. Red-MX and ox- 
MX apparently were not recoverable with LLE. ZMX and EMX did not give reproducible 
area counts for quantitation. Although the LLE recoveries were good for MCR, MBR and 
MXR, there still existed the need for recovery of the other MX-analogues and 
preconcentration to achieve lower ng/L levels in drinking water. 

Table 8. Percent recoveries of MX-analogues at 1 ng/mL by LLE 


Compounds 

Percent 

Recoveries 

MCR ring 

40% 

MCR open 

57% 

red-MX 

1 % 

MBR ring 

93% 

MXR 

81% 

ox-MXR 

0 % 

MBR open 

87% 


The MtBE extraction efficiency of MX-analogues from water was next evaluated by 
comparing recoveries after the addition of salt (granular sodium sulfate, EMScience) or acid 
[sulfuric acid (Aldrich) to pH 2] (Onstad and Weinberg, 2001). Each extraction was of a 
20-mL deionized water sample spiked to 5 pg/L with the MX-analogues. Two standard 
mixes were evaluated separately, to prevent co-elution on the gas chromatogram, the first 
one containing MX, ox-MX, and BMX-3, and the second one containing MCA, BMX-1, 
and BMX-2. Percent recoveries were calculated relative to the GC responses of derivatized 
standard mixes (Table 9). The MX-analogues were recovered poorly in the control (28 ± 
25%), with only three compounds yielding higher that 50% (MXR, ZMXR, and BEMXR- 
1). The salting-out approach did not improve extraction efficiency relative to the control 
(16 ± 17%). Acidification to pH 2 improved the MtBE extraction efficiency of both the 
open and ring forms of the MX-analogues (74 ± 10%). 


Table 9. Extraction Efficiencies of MX-analogues 


Compound 

Control 

Salt 

Acid 

MCR ring 

16% 

0 % 

82% 

MCR open 

11 % 

3% 

66 % 

MXR 

61% 

39% 

89% 

ox-MXR 

0 % 

13% 

64% 

ZMXR 

55% 

40% 

73% 

EMXR 

12 % 

14% 

61% 

BEMXR-1 

41% 

31% 

73% 

BEMXR-2 

53% 

0 % 

75% 

BEMXR-3 

0 % 

0 % 

87% 

average 

28% 

16% 

74% 

std dev 

25% 

17% 

10 % 


416 


























Solid Phase Extraction 


Solid phase extraction (SPE) was evaluated as a viable method of preconcentration 
and an alternative method of extraction to LLE. The octadecyl silane phase (Cl 8, J.T. 
Baker) was compared to LLE for recovery of MX from a 10-mL aqueous solution (100 
ng/mL MX/DIW). The aqueous sample was passed through the SPE column at a rate of < 5 
mL/min, and the solid phase was dried using a vacuum. When eluted with 1 mL of 
methanol, the Cl 8 column recovered only 25% of MX in aqueous solution. 

Using the method development guidelines of Thurman and Mills (1998), different 
solid phases and elution solvents were first compared for the recovery of a mixture of MX- 
analogues made in the elution solvent, and then solid phase recoveries of a mixture of MX- 
analogues spiked into deionized water and tap water were determined. Two different solid 
phases, Cl8 (3 mL, 500 mg) and polyamide (DPA-6S, Supelco, 6 mL, 500 mg) were each 
washed with MX-analogue solutions (40 ng/mL chlorinated MX-analogues) made 
separately in methanol (Mallinckrodt AR Anhydrous), MtBE, and 14% BF 3 /MeOH (Table 
10 ), to determine whether there would be irreversible retention of the target analytes on the 
solid phase if these were the eluting solvents used in the SPE process. The BF 3 /MeOH 
esterifying reagent dissolved the polyamide (DPA-6S) phase, and created large air pockets, 
therefore preventing further investigation of this combination. The BMX compounds were 
not included in this preliminary study. The percent recovery results follow. 


Table 10. Percent recovery of MX-analogues from Ci 8 and DPA-6S 


Compounds: 

MCR 

ring 

MCR 

open 

red- 

MX 

MBR 

ring 

MXR 

ox- 

MXR 

MBR 

open 

ZMXR 

EMXR 

C18 

spk/MtBE 

29% 

49% 

0 % 

3% 

38% 

2 % 

51% 

62% 

62% 

C18 

spk/MeOH 

108% 

59% 

0 % 

102 % 

122 % 

70% 

56% 

78% 

148% 

C18 

spk/BF3/MeOH 

60% 

53% 

0 % 

63% 

65% 

0 % 

29% 

48% 

70% 

DPA-6S 

spk/MtBE 

1 % 

2 % 

0 % 

1 % 

0 % 

0 % 

0 % 

0 % 

0 % 

DPA-6S 

spk/MeOH 

0 % 

0 % 

0 % 

0 % 

8 % 

6 % 

0 % 

0 % 

0 % 


Methanol was chosen to be the best solvent for partitioning of the MX-analogues off 
of the Cl 8 solid phase extraction columns (average 83% recovery). BF 3 /MeOH was the 
second best solvent for C18 SPE (average 42% recovery), without heating, during 
derivatization. MtBE gave similar recoveries when applied to Cl8 SPE (average 36 % 
recovery). The MX-analogues preferentially partitioned onto the DPA-6S SPE columns 
using methanol or MtBE (average 0% recovery). The spiked BF 3 /MeOH degraded the 
DPA-6S phase on contact; this is due to the derivatization reaction which releases 


417 

















hydrofluoric and boric acids. All calculated average percent recoveries were weighted down 
by zero recovery of red-MX in all cases. For compounds containing open and ring forms 
(MXR, MBR, MCR), the open forms were retained by the solid phase much more than the 
ring forms (—100% recovery of ring vs. -60% open on the Cl 8 spk/MeOH ). This was also 
evident for ox-MXR. The Cl8 reverse phase proved to be the most effective phase for 
recovery of the MX-analogues (80-100% recovery of select MX-analogues). 

Solutions of MX-analogues in deionized water (100 mL volumes at 1 pg/L MX- 
analogues/DIW) were then evaluated for recovery by Cl8 solid phase, with less favorable 
results. Table 11 highlights the recoveries of MX-analogues under neutral (no alteration, 
NA) and low pH (acidified to pH 2, AD) conditions, as well as percent breakthrough of 
columns in tandem (breakthrough from top column was detected in bottom column). 
Recovery of the MX-analogue standard solution (MeOH Mtx) from Cl 8 solid phase was 
reevaluated, this time including the BMX compounds. In this case the average percent 
recovery of the MeOH Mtx was 50-60%, much lower than the above 80-100%. Solid phase 
extraction was very poor with respect to the BMX compounds, both in the NA and AD 
solutions. Acidification helped to increase the recovery of the MX-analogues. However, 
the pH decrease also caused the ring forms of the MX-analogues to predominate. 


Table 11. Recovery of the MX-analogues from spiked DIW by SPE 


Sample label: 

Mtx-NA 

top 

Mtx-NA 

bottom 

Mtx-AD 

Top 

Mtx-AD 

bottom 

MeOH 

Mtx 

Compounds 






MCR ring 

ND 

ND 

28% 

22 % 

64% 

MCR open 

ND 

ND 

ND 

ND 

53% 

red-MX 

ND 

ND 

ND 

ND 

ND 

MBR ring 

ND 

ND 

41% 

39% 

64% 

MXR + 

UNK BMX-2 

7% 

ND 

54% 

29% 

52% 

ox-MXR 

ND 

ND 

26% 

ND 

46% 

MBR open 

ND 

6 % 

ND 

ND 

62% 

BMXR-1A 

ND 

>100% 

ND 

ND 

>100% 

BMXR-1B 

ND 

ND 

>100% 

ND 

>100% 

ZMXR 

ND 

ND 

ND 

ND 

54% 

EMXR 

ND 

ND 

16% 

ND 

40% 

BMXR-2 

>100% 

83% 

>100% 

ND 

>100% 

BEMXR-1 

ND 

ND 

ND 

ND 

57% 

BEMX-2 

ND 

ND 

6 % 

ND 

65% 

BMX-3 

ND 

ND 

ND 

ND 

ND 

BEMX-3 

ND 

ND 

ND 

ND 

42% 


ND: not detected (below 5% recovery), NA: not acidified, AD: acidified to pH 2 


418 


























A number of other solid phases (3 mL, 500 mg) were then compared to Cl 8 for 
effective recovery of MX (Table 12). An aqueous solution (260 ng/L MX and 100 ng/L 
MBA in DIW) was prepared and passed through Cyclohexyl (J.T. Baker), Cyano (J.T. 
Baker), C8 (Phenomenex Strata), C18E (Phenomenex Strata), and Cl8 (J.T. Baker) in 250 
mL quantities, and results were compared to blanks, both in duplicate. Each column was 
eluted twice with 500-pL aliquots of methanol. The methanol eluents were derivatized, 
neutralized, and hexane-extracted before analysis by GC-ECD. None of the solid phases 
recovered greater amounts of MX than Cl 8 had previously recovered (25%) from spiked 
DIW. For this reason, SPE was not considered as a practical alternative preconcentration 
method to LLE for the MX-analogues. 


Table 12. Comparison of SPE phases for MX recovery from DIW 


Solid Phase 

MX 

Recovery 

Cyclohexyl 

16% 

Cyano 

0% 

C8 

9% 

C18E 

15% 

C18 

6% 


Method Calibration Curves 

The liquid-liquid extraction method was applied to acidified (pH 2), 100 mL samples 
that were spiked with all of the MX-analogues, except ox-EMX (Figure 1) (Onstad and 
Weinberg, 2001). The chlorinated tap water samples were quenched of residual chlorine 
with ammonium sulfate (Mallinckrodt) prior to extraction. The combined 50 mL MtBE 
extracts (2 x 25 mL MtBE) were reduced to 500 pL with nitrogen gas (UHP, 99.999%). 
After derivatization of the MtBE extract and neutralization, the final hexane extract (1 mL) 
recovered only ~60% of the MXR-analogues, considering the results of the partition 
experiments above. Linearity was observed for MX and MX-analogues in deionized and 
chlorinated tap waters only at ng/L levels. Example calibration curves are shown in Figures 
11 and 12 (MX) and Figures 13 and 14 (MCA). Recoveries of MX and MCA were greatly 
reduced in the chlorinated tap water samples (Figures 11 and 12), when the detector 
response was expressed as the ratio of MX or MCA areas to the internal standard (HCB). 
However, the recoveries were more similar when the detector response was expressed as the 
ratio of MX or MCA areas to the surrogate standard (MBA) area (Figures 13 and 14). 
Reliable data is obtainable down to 50 ng/L MCA and 75 ng/L MX by liquid-liquid 
extraction (100:1 concentration factor) when 100 mL is used as the sample volume. 


419 









♦ MXRDIW * MXRTap 


a> 


<D 

> 

Q) 

CO 



Figure 11. MX Calibration Curve, using area relative to internal standard. 



Figure 12. MCA Calibration Curve, using area relative to internal standard. 


420 



















Figure 13. Calibration curve for MX, using area relative to surrogate standard. 



0 50 100 150 200 250 300 

Concentration (ng/L) 


Figure 14. Calibration curve for MCA, using area relative to surrogate standard. 


421 

















Stability in Aqueous Solutions 

In order to stabilize the levels of MX in samples upon collection, they must be 
quenched of residual chlorine to prevent further production or degradation of MX by 
chlorine, treated with a biocide to prevent microbial degradation of MX, acidified to pH 2 in 
order to prevent conversion of MX to open forms (ZMX and EMX) and degradation at high 
pH, and stored at low temperatures (less than or equal to 4°C) to prevent thermal 
degradation of MX. 

Holding temperature of samples was evaluated by storing an aqueous solution (100 
ng/mL MX/DIW) at room temperature (25°C) and in a refrigerator (4°C). The samples 
were extracted after 24 and 48 hours, using LLE at a 10:2 extraction ratio with MtBE. MX 
was more stable at the lower temperature; at 4°C, 63% MX was recovered, while at 25°C, 
only 40% MX was recovered. MX recoveries for the two storage temperatures did not 
change between 24 and 48 hours. 

The stability of MX and MCA in tap water samples was then monitored over 14 
days to determine the appropriate holding time for samples (Onstad et al., 2000). Previous 
attempts to determine holding time utilized the biocide sodium azide (NaN 3 ) in combination 
with a variety of chlorine quenching agents (ammonium sulfate, L-ascorbic acid, sodium 
sulfite, and sodium bisulfate). However, the MX-analogues could not be recovered by 
extraction, due to the reaction of sodium azide with the furanone rings in MX-analogues 
(Beccalli et ah, 2000). Therefore, the biocide was removed from the procedure. In this 
case, a 10 L sample of chlorinated tap water was spiked with MX and MCA to a 
concentration of 500 ng/L. The water was transferred to 250 mL bottles and quenched of 
residual chlorine with aqueous ammonium sulfate solution (100 pL of 40 mg/mL 
(NH^SCL) or a combination of ammonium sulfate and sulfuric acid. 

The samples were stored at 4°C and extracted in duplicate on days 0, 1,2, 4, 7, and 
14. Prior to extraction, each 250-mL sample was spiked with the surrogate standard (MBA) 
to a concentration of 500 ng/L. The samples containing only ammonium sulfate as the 
quenching agent needed to be acidified prior to extraction (to pH 3), while the other samples 
were already acidic (also pH 3). Method calibration samples at concentrations of 0 and 500 
ng/L for MX-analogues in deionized water were extracted each day of the study, in order to 
calculate concentrations of the MX-analogues in the tap water samples. The MtBE extracts 
were reduced from 100 mL to 500 pL with rotoevaporation and nitrogen gas. After 
derivatization of the MtBE extract and neutralization, the final combined 2 mL hexane 
extract (2 x 1 mL hexane) was reduced to 250 pL with nitrogen gas and then spiked with an 
internal standard, hexachlorobenzene (HCB). This process created a concentration factor of 
1000 . 


The first-order plots show that the combination of ammonium sulfate and acid for 
quenching stabilized the MX in the tap water samples only slightly longer than ammonium 
sulfate alone (Figures 15 and 16). The first-order degradation rate constants are very 
similar, as well (k~0.077 days' 1 , ti/2=9.0 days). This agrees with rates of hydrolysis at pH 
7.0 measured by Croue and Reckhow (1989) at 20°C, k = 0.9±0.5 x 10' 6 s’ 1 ( -0.07 days' 1 ) 


422 


and 1 1/2 ~ 8.9 days. The MCA components coeluted with components in the tap water 
samples and their stability could not be evaluated in this study. The immediate degradation 
of MX in tap water samples calls for rapid sample extraction and processing upon receipt of 
samples. 



Figure 15. Degradation of MX in chlorinated tap water quenched with ammonium 
sulfate. 





| _____ 

Figure 16. Degradation of MX in chlorinated tap water quenched with ammonium 
sulfate and preserved with sulfuric acid. 


Final Method for Occurrence Study Drinking Water Samples. 

The final optimized method developed for the MX analogues is shown in the first 
part of this chapter (Method Summary). 


423 

















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Kronberg, L., and R. Franzen. Determination of chlorinated furanones, hydroxyfuranones, 
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428 


CARBONYL, HALOACID, HALOACETATE, AND HALOACETAMIDE METHODS 


Methods for carbonyl, haloacetate, and haloacetamide target DBPs were developed at the 
University of North Carolina (UNC). A listing of these DBPs is presented in Table 1. For many 
of the targeted species, no chemical standards were commercially available. Therefore, synthesis 
was required for many. Proton nuclear magnetic resonance spectroscopy (NMR) and gas 
chromatography (GC) with ion trap mass spectrometry (MS) detection were used to confirm the 
identity and establish purities for these synthesized standards. The standards were stored at 
-15°C and periodically reassessed for purity. Extraction methods developed included liquid- 
liquid extraction (LLE) and solid phase extraction (SPE), which were used in combination with 
different derivatization techniques (e.g., methylation or pentafluorobenzylhydroxylamine 
[PFBHA] derivatization) and GC with electron capture detection (ECD) or mass spectrometry 
(MS) (Table 1). Liquid chromatography (LC) with electrospray ionization (ESI)-MS was also 
investigated for two of the target DBPs, but quantitative methods at the low pg/L detection limits 
were effected through the use of gas chromatography. The stability of these DBPs in water was 
also investigated 


Table 1. Target carbonyl, haloacid. 

haloacetate, and haloamide compounds 1 

Compound 

Abbreviation 

Source of 
Standard 

Purity 

Analytical Method 

3,3-dichloropropenoic acid 

DCPA 

Synthesized at 
UNC. 

>95% by 
NMR 

LLE - diazomethane 

Dimethylglyoxal (2,3- 
butanedione) 

23BD 

Aldrich 

97% 

PFBHA-LLE 

Chloroacetaldehyde 

CA 

ChemService 
and Aldrich 

50% 

solution in 

water 

PFBHA-LLE 

Bromochloroacetaldehyde 

BCA 

Can Syn 

35% 

LLE, PFBHA-LLE 

Dichloroacetaldehyde 

DCA 

TCI America 

>95% by 
GC/EI-MS 

LLE, PFBHA-LLE 

Bromochloromethyl acetate 

BCMA 

Supelco 

>99.99% 

LLE 

2-Chloroacetamide 


Aldrich 

98% 

LLE 

2,2-Dichloroacetamide 


Aldrich 

98% 

LLE 

2-Bromoacetamide 


Aldrich 

98% 

LLE 

2,2-Dibromoacetamide 


Sigma-Aldrich 

98% 

LLE 

2,2,2-Trichloroacetamide 


Aldrich 

99% 

LLE 

Trans-2-hexenal 

TH 

Acros 

99% 

PFBHA-LLE, SPE-ESI 

5-Keto-l-hexanal 

5KH 

Majestic 

Research 

-20% 

PFBHA-LLE, SPE-ESI 

Cyanoformaldehyde-oxime 

CNF 

Can Syn 

51% 

LLE 

6-Hydroxy-2-hexanone 

6HH 

Majestic 

Research 

>95% 

PFBHA-LLE, SPE-ESI 


Abbreviations: Can Syn: Synthesized by Can Syn Chem Corp (Toronto, ON, Canada); TCI 
America (Portland, Ore.); Aldrich Chemical Co. (St. Louis, Mo.); Acros Organics (Pittsburgh, 
PA); Majestic Research: Synthesized by Majestic Research (Athens, GA). 


429 

























SAMPLE COLLECTION 


Amber glass bottles (20 mL for carbonyl, haloacetate, and haloacetamide samples; 250 
mL for haloacid samples) containing a quenching agent and labeled according to sample site and 
location, quenching agent added, and date were sent in coolers to each drinking water utility for 
sampling. Samples were collected headspace-free in these vials by staff at the water utilities. 
Travel blanks were prepared in the same manner, but were pre-filled with deionized water and 
capped with no headspace. All bottles for the same sample location and site were individually 
wrapped in bubble wrap and packaged together and labeled with the sample site and location. 
Bubble-wrapped bottles were then packed into a padded cooler along with a check-list of bottles 
sent and ice packs. Once samples were collected at the utility, they were shipped back to UNC 
overnight. 


CARBONYL METHOD 

Figure 1 provides of summary of the procedure used to quantify the carbonyl DBPs in 
drinking water samples. Methods published by Yu et al. (1995) and the U.S. EPA (Method 556) 
served as the basis for the method used here. 

Concentrations of stock solutions prepared are summarized in Table 2. Dilutions were 
made using methanol (Dilution I and II) or deionized water (DIW) (Dilution III). Solutions of 
the surrogate standard, 4-fluorobenzaldehyde, were made up in methanol, and solutions of the 
internal standard (IS), 1,2-dibromopropane, were made up in hexane. Dilution III solutions 
could be used for 2-3 days. PFBHA solutions were prepared fresh for each 
derivatization/extraction. Stock solutions of all compounds, internal standard and surrogate 
standard and their dilutions were stored at 4°C when not in use. Calibration curves were created 
using different concentration ranges (in the low pg/L range) for each DBP (Table 3). 


430 


Water sample 
20 ml 



< 


< 



Derivatization 
Water bath 
2 h, 35°C 


Add 20 pL Surrogate standard 
(4-fluorobenzaldehyde, 20 mg/L) 

Add 200 mg potassium hydrogen 
phthalate 

Add 1 ml Derivatization agent 
(PFBHA, 15 mg/mL) 


Add 4 drops of H 2 S0 4 cone. 

Add 4 mL hexane + IS 
(1,2-Dibromopropane, 100 pg/L) 

Mix for 1 min 

Transfer hexane layer to another 
vial containing 3 mL 0.2 N H 2 S0 4 

Mix for 1 min 

Transfer ca. 1 ml to autosampler vial 


Figure 1. Summary of procedure used to quantify carbonyl DBPs in water. 


431 






























Table 2. Carbonyl Stock Solutions and Dilutions 


Compound 

Dilution I a 

Cone. 

(g/L MeOH) 

Dilution II a 

Cone 

(mg/L MeOH) 

Dilution III 

Cone 

(Vg/L H 2 0) 

Chloroacetaldehyde 

12.035 

120.35 

1203.50 

Bromochloroacetaldehyde 

4- 

Dichloroacetaldehyde 

0.242 

0.345 

9.68 

13.80 

96.80 

138.00 

Dichloroacetaldehyde 

2.156 

86.24 

862.40 

Tribromoacetaldehyde 

26.825 

10.73 

107.30 

7><ms-2-hexenal 

8.3 

9.96 

99.60 

6-Hydroxy-2-hexanone 

3.204 

51.26 

512.60 

5-Keto-l-hexanal 

1.106 

11.06 

110.60 

2,3-Butandione 

10.111 

10.11 

101.11 

Cyanoformaldehyde-oxime 

0.956 

9.56 

95.6 

4-Fluorobenzaldehyde 
(Surrogate Standard) 

235.44 

23.544 


1,2-Dibromopropane 
(Internal Standard) 

939.85 

9.3985 



a Solutions of the internal standard were made in hexane 


Table 3. Concentrations used for calibration curves (solutions in deionized water) 


CA 

BCA 

DCA 

TBA 

TH 

23BD 

5KH 

6HH 

CNF 

1.204 

0.097 

1.000 

0.107 

0.100 

0.101 

0.111 

0.513 

2.88 

2.407 

0.194 

2.001 

0.215 

0.199 

0.202 

0.221 

1.025 

5.8 

6.018 

0.484 

5.002 

0.537 

0.498 

0.506 

0.553 

2.563 

14.4 

12.035 

0.968 

10.004 

1.073 

0.996 

1.011 

1.106 

5.126 

28.8 

24.070 

1.936 

20.008 

2.146 

1.992 

2.022 

2.212 

10.252 

57.6 


Derivatization and Extraction 

Briefly, the pentafluorobenzylhydroxylamine (PFBHA) derivatization procedure was 
carried out as follows. Twenty mL of each drinking water sample was measured and placed into 
a 40-mL vial (2 vials per sample). Four 20-mL vials of one sample were also collected from 
each treatment plant to determine recoveries. Twenty mL of each calibration standard was also 
measured and placed into 40-mL vials (2 vials per sample). Twenty pL of the surrogate solution 
(23.5 mg/L of 4-fluorobenzaldehyde) was then spiked into each calibration and aqueous sample, 
and approximately 200 mg of potassium hydrogen phthalate was added to samples for pH 
adjustment. One mL of freshly prepared PFBHA (15 mg/mL in deionized water) was then added 
to each sample, and samples were placed in a water bath at 35°C for 2 hours. After cooling to 
room temperature, 4 drops of concentrated sulfuric acid (approximately 0.05 mL) was added to 
prevent the extraction of the unreacted PFBHA reagent, and 4 mL of the internal standard 
solution (9.4 mg/L in hexane) was added and mixed for 1 min using a vortex mixer. The 
aqueous and hexane layers were allowed to separate, and the hexane layer was transferred to a 
separate 20-mL vial that contained 3 mL of 0.2 N sulfuric acid, and was mixed for 1 min using a 

432 



































vortex mixer. Finally, a disposable pipet was used to draw off the hexane layer into a labeled 
1.8-mL autosampler vial. Prior to analysis by GC-ECD, samples were stored in the freezer 
covered with aluminum foil. 

GC-ECD Analysis 

GC analyses were carried out on a Baity GC-3 gas chromatograph. Injections of 1 pL of 
each extract were introduced via a splitless injector onto a DB-1 column (30-m, 0.25 mm ID, 
0.25 pm film thickness; J&W Scientific/Agilent, Folsom, CA). The GC temperature program 
consisted of an initial temperature of 50°C, which was held for 1 min, followed by an increase at 
a rate of 4°C /min to 250°C, followed by an increase at a rate of 3°C /min to 280°C, which was 
held for 3 min. The injector and the detector were controlled at 150 and 280°C, respectively. 
Prior to analyzing the real drinking water extracts, the internal standard solution (in hexane) and 
the pure hexane used to prepare this solution were analyzed as blanks. 

Results 

The retention times obtained for the carbonyl standards are shown in Table 4. Two 
isomers were formed for the PFBHA derivatives —syn and anti. When these isomers separated 
by GC, both retention times are given below. Figure 2 shows a representative GC 
chromatogram, which was used for one of the calibration points. Practical quantitation limits 
obtained using this method are listed in Table 5, along with typical coefficient of variations for 
triplicate analyses. 


Table 4. Retention times for PFB 

TA-derivatized DBPs 

Compound 

Abbrev. 

Retention ti 

DB-1 

me (min) 

HP-5MS 

Chloroacetaldehyde 

CA 

30.39 

18.54 

Dichloroacetaldehyde 

DCA 

32.37 

32.64 

20.55 

20.84 

Bromochloroacetaldehyde 

BCA 

35.14 

35.50 

23.70 

Cyanoformaldehyde 

CFA 

28.23 

28.35 

17.37 

Trans-2-hexanal 

TH 

37.26 

37.46 

25.74 

6-Hydroxy-2-hexanone 

6HH 

39.47 

39.90 

27.77 

28.10 

5-Keto-l-hexanal 

5KH 

39.14 

39.65 


2,3-Butanedione 

23BD 

31.57 

39.34 

4-Fluorobenzaldehyde (Surrogate) 

4FBA 

41.38 

41.69 

29.91 

30.09 

1,2-Dibromopropane (IS) 

12DBP 

13.44 

4.14 


433 





















Figure 2. GC-ECD chromatogram showing the different carbonyl-PFBHA derivatives, along with the internal standard (1,2- 
dibromopropane [2DBP]) and surrogate standard (4-fluorobenzaldehyde [4FBA]). Abbreviations given in Table 1. 


434 










































Compound 

PQL (pg/L) 

Chloroacetaldehyde 

0.2 

Dichloroacetaldehyde 

0.4 

Bromochloroacetaldehyde 

0.3 

Cyanoformaldehyde 

3.0 

Trans-2-hexanal 

0.3 

6-Hydroxy-2-hexanone 

0.3 

5-Keto-l-hexanal 

0.8 

2,3-Butanedione 

0.3 


Stability of DBPs 

In order to determine an appropriate sample handling procedure, a variety of quenching 
agents were assessed over a 7-day holding time. Although sodium sulfite appeared to maintain 
levels of carbonyl DBPs over the 14-day period, it was not chosen as the quenching agent 
because it is capable of participating in side reactions with other precursors to generate the DBPs 
studied here. Therefore, for the sake of consistency with other methods used for this study, 
ammonium sulfate, which also adequately preserved the DBPs over the 14-day period, was 
selected as the quenching agent for these compounds. 

Compound Notes 

Haloacetaldehydes. PFBHA derivatization in water generated a consistent 85% 
conversion of chloro- and dichloroacetaldehyde to the corresponding oximes in a variety of 
matrices. For the measurement of bromochloroacetaldehyde, dichloroacetaldehyde was found to 
be a major contaminant in the synthesized product; therefore, the product generated by PFBHA 
derivatization contained a mixture of 35% bromochloroacetaldehyde and 38% 
dichloroacetaldehyde. These “standards” were used to quantify the conversion of the aldehyde 
to the oxime during in situ derivatizations in water. Derivatizations showed a consistent 75% 
conversion. The sum of the syn and anti isomers used for quantitation of 
bromochloroacetaldehyde in water. 

Cyanoformaldehyde. While the PFBHA oxime standard of this species was synthesized 
and successfully characterized, many attempts at the synthesis of the target aldehyde were 
unsuccessful. Consequently, only semi-quantitative analysis of this compound could be made. 

Trans-2-hexenal. Both syn and anti oxime isomers were formed by PFBHA 
derivatization, and the sum of these peaks was used to quantify /ran5 , -2-hexenal in water. 

6-Hydroxy-2-hexanone. Both syn and anti oxime isomers were formed by PFBHA 
derivatization, and the sum of these peaks was used to quantify trans- 2-hexenal in water. 

5-Keto-l-hexanal. Both syn and anti oxime isomers were formed by PFBHA 
derivatization, and the sum of these peaks was used to quantify frYws-2-hexenal in water. 

435 














2,3-Butanedione (dimethyl glyoxal). Matrix effects suppressed the ability of the diketone 
to form a di-derivatized oxime. However, quantitation was possible by calibrating using both the 
mono- and di-oximes and summing their concentration for the overall concentration of 2,3- 
butanedione in the original water sample. 


3,3-DICHLOROPROPENOIC ACID METHOD 

Liquid-liquid extraction (LLE) and diazomethane derivatization were used with GC-ECD 
detection to quantify 3,3-dichloropropenoic acid (DCPA) in drinking water samples (a modified 
EPA Method 552 approach). A practical quantitation limit (PQL) of 0.3 pg/L was obtained. 

Extraction and Derivatization 

Samples were equilibrated to room temperature; two duplicate 20-mL samples were used 
to analyze for DCPA. Calibration standards were prepared in deionized water at concentrations 
of 1.9, 4.75, 9.5, 19, and 47.5 pg/L. Twenty mL of each of the two duplicate samples was 
measured into 40-mL vials, and 50 pL of the surrogate solution (2,3-dibromopropanoic acid, 20 
mg/mL) was added to each sample. Concentrated sulfuric acid (1.5 mL) was then added, vials 
were cooled to room temperature, and 4 mL of the internal standard (100 pg/L in MtBE) was 
added to each sample. Approximately 6 g of sodium sulfate was added to each vial and was 
mixed by vortex for at least 1 min. The upper ether layer was then transferred to a 2-mL 
volumetric flask, magnesium sulfate was added, and flasks were cooled in the refrigerator for 10 
min. 

Cold diazomethane solution (225 pL, previously prepared according to a slight 
modification of the method of Glastrup (1998)), was added to each flask and returned to the 
refrigerator for 30 min. Following this period, flasks were gently removed from the refrigerator 
and allowed to come to room temperature for 15 min. The presence of a yellow color should 
remain (indicating the presence of an excess of diazomethane reagent). A small scoop of silicic 
acid was then added to each sample to quench the excess diazomethane, and 10-15 min was 
allowed for the solid to settle. The upper ether layer was ten transferred to labeled autosampler 
vials for GC-ECD analysis. If samples could not be analyzed immediately, autosampler vials 
containing extracts were stored in the freezer. 

GC-ECD Analysis 

GC analyses were carried out on a Hewlett-Packard Model 6890 gas chromatograph 
(Hewlett-Packard/Agilent, Folsom, CA). Injections of 1 pL of each extract were introduced via 
a splitless injector onto a HP5-MS column (30-m, 0.25 mm ID, 0.25 pm film thickness; J&W 
Scientific/Agilent, Folsom, CA). The GC temperature program consisted of an initial 
temperature of 37°C, which was held for 1 min, followed by an increase at a rate of 5°C /min to 
280°C, which was held for 30 min. The injector and the detector were controlled at 180 and 
297°C, respectively. Prior to analyzing the real drinking water extracts, the internal standard 
solution (1,2-dibromopropane, 200 mg/L in MtBE) and the pure MtBE used to prepare this 

436 


solution were analyzed as blanks, surrogate standards were analyzed for retention time checks, 
calibration curve samples were analyzed in duplicate, and the internal standard was analyzed 
once more. Following the analysis of samples (in order of increasing concentration), the internal 
standard was analyzed again. 

Stability 

3,3-Dichloropropenoic acid showed good stability in water. Degradation was not 
detected when ammonium sulfate was used to quench residual chlorine, nor when the aqueous 
sample was stored for up to 14 days at 14°C. 

HALOACETATE METHOD 

Bromochloromethylacetate was the only haloacetate DBP targeted in this study. A pure 
standard was obtained from Supelco and checked for purity using NMR and GC/MS. A liquid- 
liquid extraction (LLE)-GC-ECD method similar to that of EPA Method 552.2 was used for 
quantifying bromochloromethylacetate in water, except that hexane was used in place of MtBE 
as the extraction solvent. LLE with hexane was found to provide a more consistent and higher 
recovery (92%) than MtBE (75%). No sample pretreatment or derivatization was necessary for 
this compound. The practical quantitation limit (PQL) for this compound with a 1:5 
concentration factor was determined to be 0.3 pg/L. 


Extraction 

Samples were equilibrated to room temperature; two duplicate 20-mL samples were used 
to analyze for bromochloromethylacetate in water. Calibration standards were prepared in 
deionized water at concentrations of 0.3, 1.0, 5.0, 10.0, and 25.0 pg/L generating a calibration 
curve with a median regression coefficient (r 2 ) of 0.998. Twenty mL of each of the two 
duplicate samples was measured into 40-mL vials, 4 mL of the extracting solvent (hexane) and 
100 pg/L internal standard (1,2-dibromopropane) dispensed, and approximately 6 g of sodium 
sulfate added to each vial, which was then capped and mixed by vortex for at least 1 min. The 
upper organic layer was then transferred to a 1-mL autosampler vial for analysis by GC-ECD. 
Spike recoveries were assessed on the plant effluent or average distribution system samples 
through the addition of 5 pg/L of standard. Typical spike recoveries in these samples fell in the 
range 80-110% for all samples analyzed in this project. For a single set of triplicate, spiked 
samples, the coefficient of variation was in the range of 6-10%. All plant samples were collected 
in vials containing ammonium sulfate to quench residual chlorine. During method development 
it was observed that the presence of a chloramine or chlorine dioxide residual had no effect on 
the levels of bromochloromethylacetate spiked into plant waters, provided the samples were 
stored within 24 hours of collection at 4°C and subsequently analyzed within 14 days. Chlorine- 
quenched samples (with ammonium sulfate) could be held under similar conditions without 
compromising sample integrity. 


437 


Analysis 


The GC-ECD conditions were as follows: a 30-m DB-5 column (J&W Scientific/Agilent, 
Folsom, CA) with dimensions 0.25 mm I.D. and 0.25pm film thickness) was operated under the 
following oven temperature program: initial temperature of 50 °C held for 1 min, followed by a 
temperature gradient of 4°C/min to 250°C, which was held for 3 min. The injector was operated 
in the splitless mode at a temperature of 180°C, while the pECD was held at a temperature of 
300°C. The retention time of the target compound under these conditions (and carrier gas flow- 
rate of 1 mL/min) was 6.1 min and was well resolved from other co-extracted neutral DBPs, such 
as trihalomethanes. 


HALOACETAMIDE METHODS 

The haloacetamides included in this study are listed in Table 6. Several approaches were 
attempted for these compounds including silylation, a novel liquid chromatography (LC)/MS 
method, a method involving the conversion of haloacetamides to their corresponding haloacetic 
acids by acid-catalyzed hydrolysis, and a direct liquid-liquid extraction-GC-ECD method. The 
silylation method, as described in a paper by Le Lacheur et al. (1993) resulted in a practical 
quantitation limit of 10 pg/L. The novel LC/MS method in conjunction with solid-phase 
extraction also showed relatively high detection limits (>20 pg/L). The hydrolysis approach 
appeared to be the most promising method when initially tested on standards in deionized water, 
but when tested using real drinking water samples containing natural organic matter, it resulted 
in the formation of additional halogenated by-products. Finally, a direct LLE with gas 
chromatography (GC)-electron capture detection (ECD) proved to be the best method to use for 
quantifying the haloacetamide DBPs for this Nationwide Occurrence Study. 


Table 6. Listing of haloacetamides included in this study 


Compound 

Supplier & cat. # 

Final cone, of 
stock solution 
(g/L) 

Retention Time 

By GC-ECD 

Trichloroacetamide 

Aldrich 

0.98 

25.821 

Dibromoacetamide 

SALOR(Aldrich) 

1.08 

27.226 

Dichloroacetamide 

Aldrich 

1.01 

21.799 

Monobromoacetamide 

Aldrich 

1.02 

22.84 

Monochloroacetamide 

Aldrich 

0.98 

17.55 


Silylation Method 

This method was initially tested using one of the halacetamides-dichloroacetamide. 
Three dichloroacetamide/MtBE solutions were used: 108, 54 and 1.08 mg/L. One mL of each 
solution was treated with 100 pL of N-methyl-N-(ter/-butyldimethylsilyl)trifluoroacetamide 
(MTBSTFA) and sonicated at 60°C for 1 hour. The solution was then cooled to room 


438 












temperature and stored at -20°C until analyzed by GC-ECD using a DB-5 column (J&W 
Scientific/Agilent, Folsom, CA). The reaction is shown below. 


MtBE, 60°C, 1 hour 

Cl 2 -CH-CO-NH 2 + CF 3 -CO-N(CH3)-Si(CH3) 2 -C(CH 3 ) 2 -CH3 -► 

(mol. wt. = 127) MTBSTFA 

Cl 2 CH-CO-N(CH3)-Si(CH 3 ) 2 -C(CH 3 ) 2 -CH3 
product, mol. wt. = 241 


Silyl derivatives were made at four different concentrations of dichloroacetamide in 
MtBE for use as standards. In a typical experiment, a known amount of dichloroacetamide in 2 
mL MtBE was measured into a 4-mL vial. Then, 100 pL of the silylating agent MTBSTFA was 
injected and the vial kept at 45°C for 2 hours. After cooling, the sample was analyzed by GC- 
ECD and GC/MS using a 30-m, 0.25 mm, 0.25 pm DB-5 column (J&W Scientific/Agilent, 
Folsom, CA). The operating conditions were as follows: carrier gas flow rate was 1.2 mL/min, 
initial oven temperature 50°C for 1 min then 4°C/min to 250°C; with ECD, the splitless mode 
injector temperature was 180°C and detector temperature was 300°C; with ion trap MS, initial 
injector temperature was 50°C for 1 min then rapid increase to 250°C. The trap manifold was set 
at 180°C and transfer line at 280°C. Emission current was 10 pA, mass scan range was from 50- 
650 Da, and electron multiplier voltage was 1500 V. 

The silyl-dichloroacetamide derivative eluted at approximately 15.5 min by GC/MS. 
Figures 3 shows the electron ionizaton (El) mass spectrum for the silyl-dichoroacetamide 
derivative. 



439 



















Recovery of Dichloroacetamide from Deionized Water. Six concentrations of 
dichloroacetamide in deionized warer were used. Ten mL of each solution was saturated with 
sodium sulfate in a 40-mL vial. Five mL of MtBE containing 1 OOpg/ jliL dibromopropane 
(internal standard) was added and shaken well to extract the dichloroacetamide. The ether layer 
was transferred to another vial and dried over anhydrous magnesium sulfate thoroughly before 
silylation. MTBSTFA (lOOpL) was injected into each of the vials and kept at 50°C for 1 hour. 
The solution was then cooled to room temperature and transferred to a GC vial for analysis. The 
recoveries compared to the standards were very low (4-20%) and suggested that, at least without 
additional preconcentration, the application of this method for the analysis of dichloroacetamide 
in water would be limited to a practical quantitation limit of lOpg/L. 

Because the recoveries were poor with this method, direct determination of 
dichloroacetamide from water by solid phase extraction was also attempted, but was not 
successful. 

Acid-Catalyzed Hydrolysis Method 

Another method investigated was the acid-catalyzed hydrolysis method. This method 
involves the acid-catalyzed hydrolysis of the haloacetamide to the corresponding haloacetic acid, 
as shown below for dichloroacetamide: 

CHC1 2 C0NH 2 + h 2 o -> CHCbCOOH + NH 3 

The accepted method (EPA Method 552) for haloacetic acids could then be applied before and 
after hydrolysis to determine the amount of this compound accounted for by the haloacetamide. 

For the analysis of the haloacetic acids (EPA Method 552), an aqueous sample was 
treated with concentrated sulfuric acid, saturated with salt, extracted with MtBE and methylated 
with diazomethane and determined as its ester. Assuming that the low molecular weight amide 
may undergo acid-catalyzed hydrolysis readily with concentrated sulfuric acid and the heat 
generated during the addition, this assumption was tested by making fairly concentrated 
solutions of dichloroacetamide in deionized water and subjecting to the procedure for the 
analysis of dichloroacetic acid. This procedure produced a recovery of 38 % for 
dichloroacetamide. 

In order to optimize the method, experiments were carried out to determine the effect of 
different acid concentrations on the degree of dichloroacetamide hydrolysis. The following 
scenarios were investigated on a 20 mL aqueous sample for a 2 hour reaction: at ambient 
temperature (23°C), no acid was compared to the addition of 4 mL sulfuric acid; at a water bath 
temperature of 80°C, no acid was compared to 4 and 6 mL of sulfuric acid. A 200 pg/L solution 
of dichloroacetamide was used, and if the conversion were 100 %, 201.5 pg/L of dichloracetic 
acid would be generated. Results shown in Table 7 reveal an optimum conversion with the 
addition of 4 mL sulfuric acid at 80°C. 


440 


Using the 80°C - 4 mL acid scenario, tests were then made to determine whether the 
reaction time could be reduced without significantly impacting recovery. The results are shown 
in Table 8. 


Table 7. Impact of different reaction conditions on the hydrolysis of dichloroacetamide to 


dichloroacetic acid (DCAA) 


Sample 

DCAA measured (pg/L) 

% Conversion 

Ambient no acid 

23.31 

11.57 

Ambient - 4 mL acid 

151.2 

75.04 

80°C - no acid 

115.3 

57.22 

80°C - 4 mL acid 

195.7 

97.12 

80°C - 6 mL acid 

146.0 

72.46 


Table 8. Impact of different reaction times on the hydrolysis of dichloroacetamide to 
di chloroacetic acid (DCAA) using 4 mL acid at 80°C _ 


Reaction time (hours) 

DCAA measured (pg/L) 

% Conversion 

0 

55.4 

27.49 

0.5 

175.9 

87.30 

1 

183.4 

91.02 

2 

184.4 

91.51 

3 

179.4 

89.03 

4 

177.5 

88.09 


It was apparent that a 1 hour reaction would suffice. Using this optimized set of reaction 
conditions, dichloroacetamide solutions in a concentration range from 0 to 200 pg/L were taken 
through the hydrolysis process and the resultant equivalent amount of DCAA calculated. A plot 
of these values shown in Figure 4 indicates an average 82% conversion using a linear regression. 



Figure 4. Formation of DCAA from dichloroacetamide over a wide concentration range. 

441 

































LLE-GC-ECD Method 


A final method, involving a simple liquid-liquid extraction (LLE) and GC-ECD analysis 
proved to be the best method to use for this study. A 100 mL aliquot of 200 pg/L 
dichloroacetamide in deionized water was prepared by diluting 1 mL of 20 mg/L 
dichloroacetamide in MtBE to a final volume of 100 mL with deionized water. Four 20 mL 
aliquots were measured into clean 20 mL vials with Teflon-lined screw caps. Four mL of MtBE 
and the internal standard (100 pg/L of 2,3 dibromopropane in MtBE) were added to two of the 
aliquots, while 4 mL of ethyl acetate (EtAC) was added to the two remaining aliquots. Each vial 
was vortexed for 1 min and the solvent layer allowed to separate for five min. The extracts were 
compared to a standard of dichloracetamide at the 100% recovery level of 1 mg/L. A 1-mL 
sample of the organic layer was then analyzed by GC-ECD under the following conditions: 

GC Column: 30-m, 0.25 mm ID, 0.25 pm film thickness HP5-MS (Hewlett-Packard/Agilent, 
Folsom, CA); oven temperature program - initial temperature: 37°C, held for 1 min; 5°C/min 
increase to 280°C. The injector and detector temperatures were 180 and 300°C, respectively, 
and the injector was operated in the splitless mode. The recoveries of each sample are shown in 
Table 9. 

Table 9. Recovery of dichloroacetamide by liquid-liquid extraction from deioni zed water 


Sample 

Extraction 

solvent 

Retention 
time (min) 

Peak area 

Expected 
peak area 

Recovery (%) 

1 

MtBE 

10.521 

7737.71 

33255 

23.27 

2 

MtBE 

10.521 

7509.28 

33255 

22.58 

3 

EtAC 

10.550 

19798 

33255 

59.53 

4 

EtAC 

10.552 

19163.5 

33255 

57.63 


Based on the percent recoveries, ethyl acetate appeared to be a better solvent for extracting 
dichloroacetamide from water. This approach was then expanded for the other haloacetamides 
listed in Table 6. The statistical evaluation of this method is presented in Table 10. The linear 
calibration range extended from 1 to 50 pg/L, and water samples were spiked at 5 pg/L. 


Table 10. Statistical evaluation of LLE method for haloacetamides in water 


Compound 

PQL 

(Pg/L) 

Average % CV at 1 pg/L 

Average Spike 
Recovery (%) 

Trichloroacetamide 

0.1 

8.4 

95 

Dibromoacetamide 

0.1 

6.5 

90 

Dichloroacetamide 

0.1 

5.4 

104 

Monobromoacetamide 

0.1 

10.3 

88 

Monochloroacetamide 

0.1 

11.3 

78 


442 























REFERENCES 


Methods for the Determination of Organic Compounds in Drinking Water, Supplement 7; 
Environmental Monitoring Systems Laboratory, Office of Research and Development, U.S. 

EPA: Cincinnati, OH, July 1990; EPA/600/4-90020. 

Le Lacheur, R. M., L. B. Sonnenberg, P. C. Singer, R. F. Christman, and M. J. Charles. 
Identification of carbonyl compounds in environmental samples. Environmental Science & 
Technology 27(13):2745 (1993). 

Yu, J., H. E. Jeffries, R. M. Le Lacheur. Identifying airborne carbonyl compounds in isoprene 
atmospheric photooxidation products by their PFBHA oximes using gas chromatography/ion trap 
mass spectrometry. Environmental Science & Technology 29(8): 1923 (1995). 


443 


BROADSCREEN GAS CHROMATOGRAPHY/MASS SPECTROMETRY 

(GC/MS) METHODS 


Sample Concentration 

All water samples (39 L) were concentrated by adsorption on resins (Amberlite 
XAD, Supelco). Details about the preparation and cleaning of these resins can be found 
elsewhere (Richardson et al., 1994). Water samples were acidified to pH 2 by the 
addition of hydrochloric acid prior to passage through the columns containing a 
combination of resins (XAD-8 over XAD-2). A maximum ratio of 770:1 (v/v) of water 
to resin was used to maximize the adsorption of organic compounds and to minimize 
breakthrough. The columns were eluted with ethyl acetate, and residual water was 
removed from the ethyl acetate eluents by using separatory funnels to drain off the water 
layers, followed by the addition of sodium sulfate. Samples were further concentrated by 
rotary evaporation (to approximately 5 mL), followed by evaporation with a gentle 
stream of nitrogen (to a final volume of 1 mL). 

Raw, untreated water was collected at each sampling to enable the distinction of 
chemicals that were formed as disinfection by-products (DBPs) in the treatment process 
from chemical pollutants that were already present in the raw water. In addition to the 
raw water controls, four blanks were also analyzed: (1) ethyl acetate passed through the 
XAD resins and concentrated in the same manner as the treated samples; (b) deionized, 
distilled water passed through the XAD resins and concentrated; (c) deionized, distilled 
water treated with chlorine and concentrated; and (d) deionized, distilled water treated 
with chloramine and concentrated. The latter two blanks were done to determine whether 
there were any artifacts due to reaction of secondary disinfectants with the ethyl acetate 
or with resin impurities. As compared to the raw water samples and the treated samples, 
these blanks contained relatively few compounds. 

Derivatizations 

Methylation derivatizations with boron trifluoride in methanol were used to aid in 
identifying carboxylic acids (Kanniganti et al., 1992), and 

pentafluorobenzylhydroxylamine (PFBHA) derivatizations were used to identify polar 
aldehydes and ketones (Sclimenti et al., 1990). 

GC/MS Analysis 

High-resolution GC/electron ionization (EI)-MS and GC/chemical ionization 
(CI)-MS analyses were performed on a hybrid high-resolution mass spectrometer (VG 
70-SEQ, Micromass, Inc.) equipped with a GC (Model 5890A, Hewlett-Packard- 
Agilent). The high-resolution mass spectrometer was operated at an accelerating voltage 
of 8 kV. Low-resolution analyses were carried out at 1000 resolution and high-resolution 
analyses at 10,000 resolution. Positive Cl experiments were accomplished by using 
methane gas. Injections of 1-2 pL of the extract were introduced via a split/splitless 


444 


injector onto a GC column (DB-5, 30-m x 0.25-mm ID, 0.25-pm film thickness, J&W 
Scientific-Agilent). The GC temperature program consisted of an initial temperature of 
35°C, which was held for 4 min, followed by an increase at a rate of 9°C/min to 285°C, 
which was held for 30 min. Transfer lines were held at 280°C, and the injection port was 
controlled at 250°C. Duplicate analyses were also carried out with the GC injection port 
held at 140°C to enable the analysis of trihalonitromethanes (THNMs). In previous work, 
THNMs were found to decompose at temperatures higher than 170°C (Chen et al., 2002). 

Chemical Standards 

The following chemicals were prepared synthetically and provided by Can Syn 
Chem. Corp. (Toronto, ON, Canada): dichloroiodomethane, bromochloroiodomethane, 
iododibromomethane, diiodochloromethane, diiodobromomethane, 2,2- 
dibromopropanoic acid, 3,3-dibromopropenoic acid, cis-2,3-dibromopropenoic acid, 
tribromopropenoic acid, 2-bromobutanoic acid, cis-2-bromo-3-methylbutenedioic acid, 
trans-2,3-dibromobutenedioic acid, bromonitromethane, dichloronitromethane, 
bromochloronitromethane, bromodichloronitromethane, 1,1-dibromopropanone, 1,1,1- 
tribromopropanone, 1,1 -dibromo-3,3-dichloropropanone, 1,3-dibromo-1,3- 
dichloropropanone, and l,l,3-tribromo-3-chloropropanone. 1,1,3,3- 
Tetrabromopropanone and dibromonitromethane were prepared synthetically and 
provided by Majestic Research (Athens, GA). These chemicals were used to confirm 
tentative identifications made by mass spectrometry. All other chemicals used for 
broadscreen analyses were purchased at the highest level of purity from Aldrich, Chem 
Service, and TCI America. 

Identification of DBPs 

For qualitative identification work, the criteria used for listing an identified 
compound as a DBP was its presence in the treated-water samples in quantities at least 2- 
3 times greater than in the untreated, raw water (as judged by comparing GC peak areas). 
It was important to distinguish a compound as a DBP, even if small amounts of the 
compound were present in the raw water, because many compounds that are common 
pollutants (or natural contaminants in water) have also been proven to be DBPs. 

GC/MS chromatograms were carefully analyzed for the presence of chemicals 
that were produced in the treated samples. Each mass spectrum was carefully 
background-subtracted to remove closely eluting or co-eluting peaks, after which the 
NIST, Wiley, and Athens-EPA mass spectral library databases were searched for a match 
of the unknown’s mass spectrum. Several common DBPs, such as haloacetic acid methyl 
esters, could be quickly identified through a library database match using the large NIST 
(>100,000 spectra) and Wiley databases (>200,000 spectra). In addition, the user library 
database created at the USEPA laboratory in Athens, GA (>200 spectra, mostly DBPs) 
also enabled a rapid identification of many less common DBPs, such as 1,1,3,3,- 
tetrabromopropanone and bromochloroiodomethane. Even with a definitive library 
match, however, these identifications are listed as tentative until a match of the 
unknown’s GC retention time could be made with an authentic chemical standard. Only 


445 


when both the mass spectrum and the retention time matched were the DBPs listed as 
‘confirmed’. 

Despite the large size of the library databases and the user library that had been 
created at the USEPA-Athens, there were many new DBPs identified in this study that 
required significant interpretation to enable their identification. This process involved an 
initial study and interpretation of the low resolution GC mass spectrum. Ion fragments 
and losses from the molecular ion were studied to postulate a tentative structure. The 
presence or absence of the molecular ion was determined, and CI-MS was used when the 
molecular ion was not present or to confirm a molecular ion that was present. Next, high 
resolution EI-MS analyses were made, which allowed the mass-to-charge (m/z) ratio of 
an ion to be determined to 3 decimal places. For example, by low resolution mass 
spectrometry, a molecular ion can only be assigned a nominal mass (e.g., m/z 200). With 
high resolution mass spectrometry, this ion can be measured with greater accuracy (e.g., 
m/z 200.012). With this exact mass, generally a single empirical formula (number of 
carbons, hydrogens, oxygens, nitrogens, etc.) can be assigned to the ion. High resolution 
EI-MS was used not only for the molecular ions, but also for the fragment ions, which 
generally reduced the number of possible empirical assignments from 6-8 to one. 

Once the empirical formulas were known, functional groups could be postulated 
and overall structures assigned. All possible isomers were considered when making these 
tentative assignments. When it was not possible to choose a particular isomer as the 
correct assignment for the unknown DBP, an attempt was made to purchase or obtain a 
synthetically produced, authentic chemical standards of all the possible isomers so that a 
definitive match could be made (of both mass spectra and retention time). When the 
identification of a compound was confirmed through the analysis of an authentic 
chemical standard, it was denoted in italics in this report. All other DBP identifications 
should be considered tentative. 


REFERENCES 

Chen, P. H., S. D. Richardson, S. W. Krasner, G. Majetich, and G. Glish. Hydrogen 
Abstraction and Decomposition of Bromopicrin and Other Trihalogenated Disinfection 
Byproducts by GC/MS. Environmental Science & Technology 36:3362 (2002). 


Kanniganti, R., J. D. Johnson, L. M. Ball, and M. J. Charles. Identification of 
Compounds in Mutagenic Extracts of Aqueous Monochloraminated Fulvic Acid. 
Environmental Science & Technology 26(10): 1998 (1992). 


Richardson, S. D., A. D. Thruston, Jr., T. W. Collette, T. V. Sullins, K. S. Patterson, B. 
W. Lykins, Jr., G. Majetich, and Y. Zhang. Multispectral Identification of Chlorine 
Dioxide Disinfection Byproducts in Drinking Water. Environmental Science & 
Technology 28(4):592 (1994). 


446 


Sclimenti, M. J., S. W. Krasner, W. H. Glaze, and H. S. Weinberg. Proceedings of the 
American Water Works Association Water Quality Technology Conference', American 
Water Works Association: Denver, CO, 1990. 


447 


Mass Spectra of Newly Identified DBPs 


Iodoacetic acid methyl ester 



rrVz 


Iodobromoacetic acid methyl ester 



Iodobromopropenoic acid methyl ester (1 st isomer) 



Iodobromopropenoic acid methyl ester (2 nd isomer) 



448 


















































2-Iodo-3-methylbutenedioic acid dimethyl ester 


100- 



2,2-Dibromopropanoic acid methyl ester 


10CH 


%- 


43 


» 41 

At 


59 


53 55 


45 52 


C 


60 

/ 


_ 81 
79/ 


7t S? 75 , li! 





104 

90 

100 


107 


108 

/ 


r 


109 


137 139 


135 


123 


140 

At 


165 


167 




168 


187 


185 

\ 


172 


184 




189 

/ 


w 


190 

A* 


213.215 217 244.246,248 

rn-rp-,-,-,-' |,,|I I n, I, ■! ,1 I, I , 


rrVz 


50 60 70 


80 


1 1" 1 r 1 r 11 r 


Dibromochloropropanoic acid methyl ester 


1001 

■i 


%- 


45 


55 


59 


46 

/ 


61 74 


91 


75 


i "'i ■ ■ i 

60 70 


82 


87 


108 

112 119 
115 


97102 


135 


128 


149 


140 


144 


164 


150 

/ 

-157 

4t, 


197,199 


168 177,179-190 




201 

7 217-219,221 

I. . .. 




278 


280 


....... 

90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 


nYz 


40 50 


80 


3,3-Dibromopropenoic ac id methyl ester 


100 


% 


101,106 


213 


211 

\ 


215 


W 1 T?^73 sf ^ 7ma> ®Tt W max 

[ t M r 1111 ■ ; * > 11 ; i * 1 1 * : i f 1111 - 1 , r i> » |i i rt y 1 1 ! i { 1111 | t i • 11 1 if p r ; r j n 1 1 j - H r *. j li i , 1 1 T > “J t r: i | n i p it t pr i q n > f i m tj m n f rn r ] r H ^rr -p - : i ; , t r r [ n i 1 * m | r ; n p-irrym» pT 


40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 


216 

4 


244 


242 . 


i 1 j 11 i - | I . I I | I I I I ft | I I I I | i 1 I 

190 200 210 220 230 240 


,246 

fern 


250 


449 








































































c/s-2,3-Dibromopropenoic acid methyl ester 



Tribromopropenoic acid methyl ester 



2-Bromobutanoic acid methyl ester 



/ra/7s-4-Bromo-2-butenoic acid methyl ester 


lOOi 


% 


75 


37 55 ^^60 67 74 

\38 4 2 45 | 53^\ V / \ 69 \ 

i r* 1 ; ■ i 1 p i 1 1 "It T'l '■ t r f t t ■■ f r *• t - j 1 F* 


76 


87 95 


117 
1161 118 


40 


50 


60 


70 


81 85/ 91 ~ 97 101 105 Hl'v/'" 126 ^134/ 

i r 1 > 1 1''''. 11 1 1 ■' 1 '; 1 ' 1 < (' 1 ''—’ ''' '' , ' 1 < 1 11 1 ' 'I'' i 'i 1 11 r ' 


140147 
\^149 


178 


80 


90 


100 


110 


120 


130 


140 


150 


160 


170 


180 


rriz 


180 


450 









































c/s-4-Bromo-2-butenoic acid methyl ester 



2,3-Dibromo-2-butenoic acid methyl ester 



Bromodichlorobutenoic acid methyl ester 



Bromochloro-4-oxopentanoic acid methyl ester 



451 





































Dibromo-4-oxopentanoic acid methyl ester 


100 - 


43 


%\ 


39 


41 






5 759 fi7 ^ 89 107 m 


137.139 


■'¥—r 

40 50 60 70 80 


123.125 

- ‘r^ T Ituv l' 


143149.151 ^ 175^177 186.188 201 Z \213 227 , 229 244 246 


210 _ 






257.259265 


286 288 290 


90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 


rrVz 


Bromoheptanoic acid methyl ester 



Bromochloroheptanoic acid methyl ester (2 nd isomer) 



Dibromoheptanoic acid methyl ester 


100 - 




5 


59 


39 

68 

51 53 

\ 

♦PI,, 

Ji 


69 


125 


98 


78 -fcir f T i f 


.126 

1 


153 


141 


156 

/ 


157 

/ 


173 


184 


185 

Y 

I 


161.162 1177 i / 86 221^223 229 


40 


60 


80 


100 


120 


140 


160 


180 


200 


220 


240 


^fr 273 3 00^30 2.304 ^ 

260 280 300 320 


452 

























































Bromochlorononanoic acid methyl ester 


100 - 


*1 


J 38 


55 


59 87 


115 


92 

M 98 106 


40 50 60 70 


119 

11 |< 120 131 


145 
141 |-.146 


159 


163 191 ^205,207 ^ 

1 . . . 'I ' 1 


225227 


229 


80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 


t m/z 


2-Bromobutenedioic acid dimethyl ester 



m/z 


c/s-2-Bromo-3-methylbutenedioic acid dimethyl ester 



^ra/7s-2,3-Dibromobutenedioic acid dimethyl ester 



453 














































Iodobutanal 


100- 


198 



Dichloropropenal 



4-Chloro-2-butenal 



l-Bromo-l,3,3-trichloropropanone 



454 









































Ion Trap Mass Spectra (El) of Halogenated Furanone Standards 


Red-MX [3-Chloro-4-(dichloromethyl)-2(5H)-furanone] 



MX ester [3-Chloro-4-(dichloromethyl)-5-methoxy-2(5H)-furanone] 




455 















































EMX ester [Methyl (2 J £)-2,4,4-trichloro-3-(dimethoxymethyl)-2-butenoate] 



ox-MX ester [Dimethyl (2Z)-2-chloro-3-(dichloromethyl)-2-butenedioate] 



Mucochloric acid (ring) 3,4-dichloro-5-methoxy-2(5//)-furanone 



456 


















































































Mucochloric acid (open) [Methyl (2£)-2,3-dichloro-4,4-dimethoxy-2-butenoate] 


193 



Mucobromic acid (ring) [3,4-dibromo-5-methoxy-2(5//)-furanone] 



Mucobromic acid (open) [(2£)-2,3-dibromo-l,l,4-trimethoxy-2-butene] 



457 


















































BMX-1 ester (isomer A) [4-[bromo(chloro)methyl]-3-chloro-5-methoxy-2(5//)-furanone] 



BMX-1 ester (isomer B) [4-[bromo(chloro)methyl]-3-chloro-5-methoxy-2(5//)-furanone] 



BEMX-1 ester [Methyl (2£)-4-bromo-2,4-dichloro-3-(dimethoxymethyl)-2-butenoate] 



458 


















































































BMX-2 ester [3-chloro-4-(dibromomethyl)-5-methoxy-2(5//)-furanone] 

211 

100%-j 


7 5 %— 



BEMX-2 ester [Methyl (2£)-4,4-dibromo-2-chloro-3-(dimethoxymethyl)-2-butenoate] 



BMX-3 ester [3-bromo-4-(dibromomethyl)-5-methoxy-2(5//)-furanone] 

255 

ioo%-j i 


75 %— 


4 

- 


j 

J 

4 



459 








































































BEMX-3 ester [Methyl (2 J £)-2,4,4-tribromo-3-(dimethoxymethyl)-2-butenoate] 



460 























vvEPA 

United States 
Environmental Protection 
Agency 

National Exposure 
Research Laboratory 
Athens, GA 30605 

Official Business 
Penalty for Private Use 
$300 

EPA/600/R-02/068 
September 2002 


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LIBRARY OF CONGRESS 



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